WO2022253254A1 - 一种植物生物质基活性鞣剂的制备方法 - Google Patents

一种植物生物质基活性鞣剂的制备方法 Download PDF

Info

Publication number
WO2022253254A1
WO2022253254A1 PCT/CN2022/096522 CN2022096522W WO2022253254A1 WO 2022253254 A1 WO2022253254 A1 WO 2022253254A1 CN 2022096522 W CN2022096522 W CN 2022096522W WO 2022253254 A1 WO2022253254 A1 WO 2022253254A1
Authority
WO
WIPO (PCT)
Prior art keywords
plant biomass
tanning agent
based active
preparation
active tanning
Prior art date
Application number
PCT/CN2022/096522
Other languages
English (en)
French (fr)
Inventor
林炜
肖远航
王春华
蒋敏
Original Assignee
四川大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 四川大学 filed Critical 四川大学
Publication of WO2022253254A1 publication Critical patent/WO2022253254A1/zh

Links

Images

Classifications

    • 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
    • C14C3/10—Vegetable tanning
    • C14C3/12—Vegetable tanning using purified or modified vegetable tanning agents

Definitions

  • the invention belongs to the technical field of synthesis of clean tanning materials, and in particular relates to a preparation method of a plant biomass-based active tanning agent.
  • Tanning is the process of turning raw hides into leather through tanning agents, and is a key process in the process of leather making. Because chrome tanned leather has good comprehensive properties, chrome tanning method has always occupied a dominant position in the leather tanning process, but the Cr(III) salt used in chrome tanned leather is easily oxidized to Cr(VI) under certain conditions, making chromium The tanning method faces difficulties and challenges such as the potential environmental and health risks of Cr(VI) and the environmental pressure of tanning waste disposal.
  • aldehyde tanning agents and resin tanning agents will produce the risk of free formaldehyde during use.
  • Formaldehyde can irritate the mucous membrane of the respiratory tract. Inhaling more formaldehyde will cause suppurative edema of the lungs, and it will irritate the skin and cause burns.
  • the invention provides a preparation method of plant biomass-based active tanning agent.
  • the present invention adopts the following technical solutions to realize, and the specific operation method is as follows:
  • the emulsifier is OP-10 (polyoxyethylene octylphenol ether-10), Tween-80 (polyoxyethylene sorbitan monooleate), Span-80 (sorbitan Alcohol fatty acid ester) and AEO-7 (fatty alcohol polyoxyethylene ether) or a mixture of several.
  • the plant biomass compound is one of gallic acid, ellagic acid, ericonic acid, catechin, proanthocyanidin and tannic acid.
  • the low temperature reaction condition is one of low temperature mechanical stirring, low temperature ultrasonic treatment and low temperature microwave irradiation.
  • the temperature of the low temperature reaction condition is 0°C, 3°C or 5°C.
  • the introduction of carboxyl groups, hydroxyl groups, etc. into the molecular structure of the plant biomass-based active tanning agent can promote the coordination and cross-linking of collagen and non-chromium metal ions, resulting in a good synergistic tanning effect.
  • the invention provides the plant biomass-based active tanning agent prepared by the preparation method described in the above technical scheme.
  • the present invention uses plant biomass compound as the reaction matrix, utilizes the special structure and reactivity of cyanuric chloride to make it undergo nucleophilic substitution reaction to prepare an environment-friendly active tanning agent, wherein the cyanuric chloride is a reactive
  • the substrate and emulsifier can improve the dispersion of cyanuric chloride in water, and the prepared plant biomass-based active tanning agent can endow the leather with good hygrothermal stability and physical properties, which is conducive to the clean production and sustainable production of leather.
  • Development Adopt the preparation method of plant biomass-based active tanning agent provided by the invention, have the following advantages:
  • plant biomass compounds are used as raw materials for preparing active tanning agents, which belong to natural products, have a wide range of sources, are safe, environmentally friendly, non-toxic, economical and practical, and conform to the clean production and sustainable development strategy of tanning;
  • Active chlorine is introduced into the molecular structure of the prepared plant biomass-based active tanning agent, which can covalently bond with collagen amino groups, and has higher reactivity compared to the hydrogen bond between the phenolic hydroxyl group and collagen in the vegetable tanning agent structure , and contains active groups such as carboxyl and hydroxyl groups, which can not only endow the finished leather with good moisture and heat resistance stability, but also promote the combination between non-chrome metal tanning agents and collagen, resulting in a better synergistic tanning effect;
  • the prepared plant biomass-based active tanning agent is based on plant biomass compounds of different molecular weights, so that its molecular weight is in a multi-level gradient, corresponding to the multi-layer structure of skin collagen fibers, and then the active tanning agent is in the skin collagen A balance between penetration and bonding is reached in the structure.
  • Fig. 1 is the infrared absorption spectrum analysis figure of plant biomass-based active tanning agent in embodiment 1, and plant biomass used is gallic acid;
  • Fig. 2 is the mass spectrum analysis diagram of the plant biomass-based active tanning agent in Example 1, and the plant biomass used is gallic acid.
  • Fig. 1 is the infrared absorption spectrum analysis figure of plant biomass-based active tanning agent in embodiment 1, as can be seen from Fig. 1, 794cm -1 place is the stretching vibration absorption peak of C-Cl, 1400cm -1 , 1468cm -1 and 1564cm -
  • One is the stretching vibration absorption peak of triazine ring or benzene ring
  • the stretching vibration absorption peak of -OH is at 2923 ⁇ 3215cm -1
  • the absorption peak of COC (ether bond) also appeared at 1 , which indicated that the nucleophilic substitution reaction between gallic acid and cyanuric chloride occurred successfully.
  • Fig. 2 is the mass spectrometry analysis diagram of the plant biomass-based active tanning agent in Example 1. It can be seen from Fig. 2 that the molecular mass (m/z: 338.9) of the tanning agent measured by the mass spectrometer and its chemical structural formula (C 10 H 4 Cl 2 N 3 O 5 Na) consistent with the exact molecular weight. It is further proved that the plant biomass-based active tanning agent is successfully synthesized by the method of the present invention.
  • the average particle size and hydrodynamic radius Rh of the plant biomass-based active tanning agent prepared in Example 1 are ⁇ 95nm and ⁇ 76nm respectively, and there is only one peak, and its PDI is ⁇ 0.4, which belongs to the medium dispersion range
  • the particle diameters of the plant biomass-based active tanning agents prepared in Examples 1-3 are all below 500nm in aqueous solution, indicating that they have good penetration performance and dispersion stability during the tanning process.
  • Test example 2 Tanning performance detection
  • the plant biomass-based active tanning agent prepared in Examples 1-3 was used to directly tan the softened bare hide without pickling.
  • the specific tanning process is as follows: the raw materials used in the tanning process are based on the weight of liming hide, the control liquid ratio (water volume/tare weight) is 0.7, the drum temperature is room temperature (25°C), and 10% plant biomass-based active tanning agent is used to directly Act on the softened leather, turn it for 2 hours to make it fully penetrate into the leather fiber, then add 50% hot water (water temperature: 60°C) twice, turn it at 40°C and 45°C for 2h and 4h respectively, To promote the combination of plant biomass-based active tanning agent and skin collagen; finally let it stand overnight, wash with water for 30 minutes the next day, and get out of the drum.
  • Shrinkage temperature test use a shrinkage temperature tester to measure the shrinkage temperature (T s ) of softened leather and plant biomass-based active tanning agent tanned leather, specifically hang the sample (10mm ⁇ 60mm) vertically in distilled water at 2°C/min Heating at the heating rate until the sample shrinks is recorded as the T s of the crust leather.
  • T s shrinkage temperature
  • the shrinkage temperature of the obtained crust leather reaches 74 to 78°C, which is significantly higher than the shrinkage temperature of the softened leather ( ⁇ 58°C). It shows that the plant biomass-based active tanning agent can endow the leather with good moisture and heat stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

本发明公开了一种植物生物质基活性鞣剂的制备方法，采用三聚氯氰和植物生物质在低温反应条件下，通过亲核取代反应合成环保型植物生物质基活性鞣剂。本发明所得活性鞣剂在常温下的外观为白色或浅棕色乳状液，其结构中引入大量羟基、羧基、酯基等活性基团，赋予皮革良好的耐湿热稳定性和物理性能，与金属鞣剂具有较好的协同作用。同时避免了皮革中六价铬和游离甲醛带来的健康与环境风险。

Description

一种植物生物质基活性鞣剂的制备方法
本申请要求于2021年06月03日提交中国专利局、申请号为CN202110621604.8、发明名称为“一种植物生物质基活性鞣剂的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于清洁化制革材料合成技术领域，具体涉及一种植物生物质基活性鞣剂的制备方法。
背景技术
鞣制是通过鞣剂使生皮变为革的过程，是制革加工过程中的关键工序。因铬鞣革具有良好的综合性能而使铬鞣法在皮革鞣制工艺中一直占据主导地位，但铬鞣革使用的Cr(III)盐在一定条件下易被氧化为Cr(VI)，使铬鞣法面临着Cr(VI)潜在的环境与健康风险和制革废弃物处理的环境压力等难题与挑战。随着全球范围内对环境保护和消费者健康的日益重视，世界各国的法规与政策对皮革制品中Cr(VI)的限量也日益严格，尤其在2014年欧盟委员会修订的《化学品的注册、评估、授权和限制》(Registration,Evaluation,Authorization and Restriction ofChemicals，简称REACH)法规中，将欧盟范围内皮革制品中的Cr(VI)含量限制在3mg/kg。因此，开发环境友好的无铬鞣化学品及配套技术对制革清洁化生产和可持续发展显得至关重要。
在开发无铬鞣剂及配套技术的过程中，有机鞣剂的开发与应用一直是制革工业不可或缺的重要部分。目前主要有植物鞣剂、醛类鞣剂、合成鞣剂和树脂鞣剂等，但其单独鞣革无法同时满足皮革制品的生态性和使用性能的要求。其中醛类鞣剂和树脂鞣剂在使用过程中会产生游离甲醛的风险，甲醛对呼吸道粘膜有刺激作用，吸入较多甲醛会使肺部化脓水肿，而且会刺激皮肤，引起灼伤。目前，中国、德国、法国、荷兰、日本等国家，以及欧盟、国际环保纺织协会等组织均对皮革中的甲醛制定了从20mg/kg到1500mg/kg不等的明确规定。并且合成鞣剂和丙烯酸类鞣剂等的制备原料中含有不可再生的石油裂解产物，可导致环境污染和碳排放问题。因此近年来，开发环保型植物生物质基活性鞣剂及鞣法成为目前无铬鞣研究 的重点。
发明内容
本发明提供一种植物生物质基活性鞣剂的制备方法。为达到上述目的，本发明采用以下技术方案来实现，具体操作方法如下：
准确称取一定量三聚氯氰置于装有蒸馏水的反应瓶中，滴加适量乳化剂，在低温反应条件下充分搅拌均匀；逐滴滴加植物生物质化合物水溶液，其中三聚氯氰与植物生物质化合物水溶液中植物生物质化合物的摩尔比为(1.0～3.0)：1；并同时滴加碱溶液控制反应pH为4.0～8.0，搅拌反应4.0～8.0h；然后将反应物低温静置过夜，得到白色或浅棕色乳液，即植物生物质基活性鞣剂。
优选地，所述的乳化剂为OP-10(聚氧乙烯辛基苯酚醚-10)、吐温-80(聚氧乙烯脱水山梨醇单油酸酯)、司盘-80(失水山梨糖醇脂肪酸酯)和AEO-7(脂肪醇聚氧乙烯醚)中的一种或几种的混合物。
优选地，所述的植物生物质化合物为没食子酸、鞣花酸、橡椀酸、儿茶素、原花青素和单宁酸中的一种。
优选地，所述的低温反应条件为低温机械搅拌、低温超声处理和低温微波辐照中的一种。
优选地，所述的低温反应条件的温度为0℃、3℃或5℃。
优选地，所述的植物生物质基活性鞣剂分子结构中引入羧基、羟基等，可促进胶原与非铬金属离子的配位交联，产生良好的协同鞣制作用。
本发明提供了上述技术方案所述制备方法制备得到的植物生物质基活性鞣剂。
本发明以植物生物质化合物为反应基体，利用三聚氯氰的特殊结构与反应活性，使其发生亲核取代反应制备出一种环保型活性鞣剂，其中，所述三聚氯氰为反应底物，乳化剂能够提高三聚氯氰在水中的分散，并且所制备的植物生物质基活性鞣剂可赋予皮革良好的湿热稳定性和物理性能，有利于制革的清洁化生产和可持续发展；采用本发明提供的植物生物质基活性鞣剂的制备方法，具有以下优点：
1)本发明中采用植物生物质化合物作为制备活性鞣剂的原料，属于天然产物，来源广泛，并且安全环保无毒、经济实用，符合制革的清洁化生 产和可持续发展战略；
2)制备的植物生物质基活性鞣剂分子结构中引入活性氯，可与胶原氨基产生共价结合，相对于植物鞣剂结构中酚羟基与胶原间的氢键作用，具有更高的反应活性，并且含有羧基、羟基等活性基团，既可赋予成革良好的耐湿热稳定性，也可促进非铬金属鞣剂与胶原之间的结合，产生较好的协同鞣制效应；
3)制备的植物生物质基活性鞣剂依据不同分子质量的植物生物质化合物为基体，使其分子量处于多层级梯度，与皮胶原纤维的多层结构相对应，进而使活性鞣剂在皮胶原结构中达到渗透与结合的平衡点。
附图说明
图1为实施例1中植物生物质基活性鞣剂的红外吸收光谱分析图，所用植物生物质为没食子酸；
图2为实施例1中植物生物质基活性鞣剂的质谱分析图，所用植物生物质为没食子酸。
具体实施方式
实施例1
准确称取0.1mol三聚氯氰置于装有适量蒸馏水的反应瓶中，滴加适量乳化剂，控制反应温度为3℃，逐滴滴加0.1mol没食子酸的碱溶液，并同时滴加碱性溶液控制反应pH为6.5，机械搅拌反应6.0h；低温静置过夜，得到白色乳液，即植物生物质基活性鞣剂。
图1为实施例1中植物生物质基活性鞣剂的红外吸收光谱分析图，由图1可知，794cm -1处为C-Cl的伸缩振动吸收峰，1400cm -1、1468cm -1和1564cm -1处为三嗪环或苯环的伸缩振动吸收峰，羧基结构中C＝O的伸缩振动吸收峰在1704cm -1处，2923～3215cm -1处为-OH的伸缩振动吸收峰，并且1204cm -1处也出现了C-O-C(醚键)的吸收峰，这表明没食子酸与三聚氯氰成功发生亲核取代反应。
图2为实施例1中植物生物质基活性鞣剂的质谱分析图，由图2可知，经质谱仪测得的鞣剂分子质量(m/z:338.9)与其化学结构式(C 10H 4Cl 2N 3O 5Na)的精确分子量相一致。进一步证明采用本发明方法成功合成植物生物质基活性鞣剂。
实施例2
准确称取0.3mol三聚氯氰置于装有适量蒸馏水的反应瓶中，滴加适量乳化剂，控制反应温度为5℃，逐滴滴加0.1mol鞣花酸的碱溶液，并同时滴加碱性溶液控制反应pH为7.0，超声处理反应4.0h；低温静置过夜，得到浅棕色乳
实施例3
准确称取0.2mol三聚氯氰置于装有适量蒸馏水的反应瓶中，滴加适量乳化剂，控制反应温度为0℃，逐滴滴加0.1mol单宁酸的碱溶液，并同时滴加碱性溶液控制反应pH为6.0，微波辐照反应5.0h；低温静置过夜，得到浅棕色乳液，即植物生物质基活性鞣剂。
测试例1粒径检测
取一滴实施例1～3反应后所得乳液，采用去离子水稀释至浓度为0.1g/L，经过0.45μm过滤头过滤后注入样品池中，采用纳米粒度仪在25℃条件下测定植物生物质基活性鞣剂的流体力学半径(R h)和多分散指数(PDI)。具体结果见表1。
表1实施例1～3中植物生物质基活性鞣剂的平均粒径、粒径分布和多分散指数
Figure PCTCN2022096522-appb-000001
由表1可知，实施例1制备的植物生物质基活性鞣剂的平均粒径和流体力学半径R h分别为～95nm与～76nm，且只有一个峰，其PDI为～0.4属于中等的分散范围；实施例2和3制备的植物生物质基活性鞣剂的平均粒径增大，分别为～110nm与～409nm，且出现两个峰，对应流体力学半径R h为～25nm和～112nm(PDI：0.5)，以及～74nm和～454nm(PDI：0.6)。由此可知，实施例1～3制备的植物生物质基活性鞣剂在水溶液中的粒径均在500nm以下，表明其在鞣革过程中具有良好的渗透性能和分散稳定 性。
测试例2鞣制性能检测
采用实施例1～3制备的植物生物质基活性鞣剂，直接对软化裸皮鞣制，无需浸酸。具体鞣制工艺如下：鞣制过程用料基准以浸灰皮重量计，控制液比(水量/皮重)为0.7，转鼓温度为室温(25℃)，采用10％植物生物质基活性鞣剂直接作用于软化皮，转动2h后使其完全渗透于皮革纤维中，然后分两次加入50％的热水(水温：60℃)，分别在温度为40℃和45℃条件下转动2h和4h，以促进植物生物质基活性鞣剂与皮胶原的结合；最后静置过夜，次日水洗30min，出鼓搭马。
收缩温度测试：采用收缩温度测试仪测定软化皮和植物生物质基活性鞣剂鞣革的收缩温度(T s)，具体是将样品(10mm×60mm)垂直悬挂在蒸馏水中，以2℃/min的升温速率加热，直至样品收缩时的温度记为坯革的T s。具体结果见表2。
表2实施例1～3中植物生物质基活性鞣剂鞣制皮革的收缩温度
样品 软化皮 实施例1 实施例2 实施例3
收缩温度/℃ 58 77 74 78
由表2可知，通过将实施例1～3中植物生物质基活性鞣剂应用于皮革鞣制，所得坯革收缩温度达到74～78℃，明显高于软化皮的收缩温度(～58℃)，表明植物生物质基活性鞣剂可赋予皮革良好的耐湿热稳定性。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (7)

  1. 一种植物生物质基活性鞣剂的制备方法，其特征在于，具体操作步骤如下：
    称取定量三聚氯氰和蒸馏水置于反应瓶中，滴加适量乳化剂，在低温反应条件下，使其分散均匀，然后逐滴滴加植物生物质化合物水溶液，其中三聚氯氰与植物生物质化合物水溶液中植物生物质化合物的摩尔比为(1.0～3.0)：1；并同时滴加碱溶液控制反应pH为4.0～8.0，滴加完毕后，继续反应4～8h；然后将反应物低温静置过夜，得到白色或浅棕色乳液，即植物生物质基活性鞣剂。
  2. 根据权利要求1所述的一种植物生物质基活性鞣剂的制备方法，其特征在于，所述的乳化剂为聚氧乙烯辛基苯酚醚-10、聚氧乙烯脱水山梨醇单油酸酯、失水山梨糖醇脂肪酸酯和脂肪醇聚氧乙烯醚中的一种或几种的混合物。
  3. 根据权利要求1所述的一种植物生物质基活性鞣剂的制备方法，其特征在于，所述的植物生物质化合物为没食子酸、鞣花酸、橡椀酸、儿茶素、原花青素和单宁酸中的一种。
  4. 根据权利要求1所述的一种植物生物质基活性鞣剂的制备方法，其特征在于，所述的低温反应条件为低温机械搅拌、低温超声处理和低温微波辐照中的一种。
  5. 根据权利要求1或4所述的一种植物生物质基活性鞣剂的制备方法，其特征在于，所述的低温反应条件的温度为0℃、3℃或5℃。
  6. 权利要求1～5任一项所述制备方法制备得到的植物生物质基活性鞣剂。
  7. 权利要求6所述的植物生物质基活性鞣剂在制革中的应用，其特征在于，所述的植物生物质基活性鞣剂分子结构中引入羧基和羟基，促进胶原与非铬金属离子的配位交联，产生良好的协同鞣制作用。
PCT/CN2022/096522 2021-06-03 2022-06-01 一种植物生物质基活性鞣剂的制备方法 WO2022253254A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110621604.8A CN113278746B (zh) 2021-06-03 2021-06-03 一种植物生物质基活性鞣剂的制备方法
CN202110621604.8 2021-06-03

Publications (1)

Publication Number Publication Date
WO2022253254A1 true WO2022253254A1 (zh) 2022-12-08

Family

ID=77283210

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/096522 WO2022253254A1 (zh) 2021-06-03 2022-06-01 一种植物生物质基活性鞣剂的制备方法

Country Status (2)

Country Link
CN (1) CN113278746B (zh)
WO (1) WO2022253254A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113278746B (zh) * 2021-06-03 2022-05-17 四川大学 一种植物生物质基活性鞣剂的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5417723A (en) * 1993-03-25 1995-05-23 Bayer Aktiengesellschaft Use of ester urethanes for retanning
CN108892649A (zh) * 2018-06-11 2018-11-27 陕西科技大学 一种改性氨基酸衍生物鞣剂的制备方法
CN109943670A (zh) * 2019-01-31 2019-06-28 四川大学 一种高活性有机鞣剂单宁酸不浸酸无铬结合鞣法
CN111118233A (zh) * 2019-12-24 2020-05-08 温州大学 一种含水杨酸结构的有机氯鞣剂及其制备方法
CN113278746A (zh) * 2021-06-03 2021-08-20 四川大学 一种植物生物质基活性鞣剂的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108085434B (zh) * 2017-12-29 2020-11-17 温州大学 一种皮革用有机鞣剂及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5417723A (en) * 1993-03-25 1995-05-23 Bayer Aktiengesellschaft Use of ester urethanes for retanning
CN108892649A (zh) * 2018-06-11 2018-11-27 陕西科技大学 一种改性氨基酸衍生物鞣剂的制备方法
CN109943670A (zh) * 2019-01-31 2019-06-28 四川大学 一种高活性有机鞣剂单宁酸不浸酸无铬结合鞣法
CN111118233A (zh) * 2019-12-24 2020-05-08 温州大学 一种含水杨酸结构的有机氯鞣剂及其制备方法
CN113278746A (zh) * 2021-06-03 2021-08-20 四川大学 一种植物生物质基活性鞣剂的制备方法

Also Published As

Publication number Publication date
CN113278746A (zh) 2021-08-20
CN113278746B (zh) 2022-05-17

Similar Documents

Publication Publication Date Title
WO2022253254A1 (zh) 一种植物生物质基活性鞣剂的制备方法
CN100545343C (zh) 轻薄天然纤维材料的阻燃处理方法
CN104017920B (zh) 一种无甲醛氨基树脂复鞣剂
CN107118357A (zh) 一种儿茶酚壳聚糖自愈合水凝胶材料及其制备方法
Wang et al. Sustainable utilization of corn starch resources: A novel soluble starch-based functional chrome-free tanning agent for the eco-leather production
CN109821574A (zh) 一种铕基金属有机骨架材料Eu-MOF及其制备方法、刚果红染料光催化降解方法
CN107828923B (zh) 一种有机胺协同环氧树脂组合物鞣剂鞣制羊皮的方法
CN102492079A (zh) 多羧酸共聚物联合蒙脱土制备纳米复合高吸收铬鞣助剂的方法
CN106395915B (zh) 一种聚合氯化硫酸铁的合成方法
CN113638225B (zh) 一种三嗪类抗紫外线整理剂及其制备方法
CN107254141A (zh) 阻燃剂和涤纶以及阻燃环氧树脂固化物及其制备方法
CN106799209A (zh) 一种重金属铅离子吸附用改性二氧化硅微球
CN109502678A (zh) 一种印染污水处理剂及其制备方法
CN103627827B (zh) 一种鳄鱼皮的无铬鞣制方法
CN109943670B (zh) 一种高活性有机鞣剂单宁酸不浸酸无铬结合鞣法
CN106241937A (zh) 一种用于饮用水的吸附剂
CN110128613A (zh) 一种用于高透水汽性皮革的水性聚氨酯
Deng et al. Study on environmental-friendly dyeing processes of fast-growing plantation veneers
CN105800710B (zh) 一种阴离子染料废水处理剂
CN104589444A (zh) 碱性硅溶胶固色剂及其制备方法
CN103265705A (zh) 一种织物表面处理剂的制备方法
CN113969032A (zh) 一种紫外屏蔽亚克力单宁酸复合材料及其制备方法和用途
CN101891613A (zh) 甲基丙烯酸羟乙酯的制备方法
CN110952334A (zh) 一种增强型复合材料芳纶纤维织物及其制备方法
CN110627948A (zh) 一种双键化丁香酚改性苯丙乳液及其制备方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 17919176

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22815298

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22815298

Country of ref document: EP

Kind code of ref document: A1