CN112778206B - 一种含酮磺酸根结构的高吸收铬鞣助剂的制备方法与应用 - Google Patents
一种含酮磺酸根结构的高吸收铬鞣助剂的制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种含酮磺酸根结构的高吸收铬鞣助剂及其制备方法与应用,该助剂为含酮羰基咪唑的磺酸衍生物;本发明还公开了含酮磺酸根结构的高吸收铬鞣助剂的制备方法和应用;本发明所提供的高吸收铬鞣助剂能够在皮胶原上通过酮羰基引入磺酸根,增加铬的配位点位,提高三价铬的吸收,减少铬鞣废水中三价铬的浓度,实现高吸收铬鞣,推动制革产业的清洁化生产;本发明操作简单,为高吸收铬鞣助剂的研究提供了一种新思路。
Description
技术领域
本发明属于皮革铬鞣助剂技术领域,具体涉及一种含酮磺酸根结构的高吸收铬鞣助剂的制备方法与应用。
背景技术
铬鞣是迄今为止皮革制造中最重要且应用最广泛的鞣制方法,它赋予皮革最高的热稳定性,舒适的手感和优异的成革性能,目前在制革工业中占据绝对主导地位,无法被其他鞣制方法替代。然而,传统鞣制工艺中,铬鞣剂的吸收率通常只有70%左右,鞣制后会产生高浓度的含铬废水,造成大量铬鞣剂损失。这不仅增加了环境污染负荷和废水处理成本,也造成了极大的资源浪费。由于铬污染物对环境的不利影响,制革业已被列为高污染行业之一。因此,如何在鞣制过程中最大可能地提高铬的吸收量和铬鞣剂的利用率,实现高吸收铬鞣,是近年来制革学术界和工业界广泛关注的问题,也是保证制革工业持续发展迫切需要解决的关键科技问题(陈博,张辉,强西怀,等.高吸收铬鞣助剂的研究进展[J].中国皮革,2019,48(04):41-46;陈博,张辉,强西怀,等.羧基化改性水解胶原蛋白铬鞣助剂的制备及其性能[J].陕西科技大学学报,2019,37(5):27-32)。
高吸收铬鞣旨在通过提高鞣制过程中铬鞣剂在皮革中的吸收率至80%~98%,降低铬鞣废液的三价铬的含量,从源头上实现铬的高吸收率,该类化学品被称为高吸收铬鞣助剂。高吸收铬鞣助剂一般在浸酸或鞣制阶段加入,对目前常规制革工艺影响不大,适用范围较广。胶原改性是实现高吸收铬鞣最常用的方法之一,通过引入多种官能团(醛基、羧基、氨基、羟基等),增加皮胶原与铬(III)配位点位,实现铬鞣剂的高吸收,减少废液中铬的排放。
强西怀等应用乙醛酸化合物对皮胶原进行化学改性,在皮胶原大分子侧链上引入羧基,从而增加铬鞣剂与皮胶原纤维的结合点。废铬液中的铬含量降低为0.63g/L,铬吸收率提升至91.1%,减少铬粉用量40%-50%。(强西怀,李闻欣,俞从正,等.乙醛酸助铬鞣应用工艺的研究[J].中国皮革,2002,31(07):28-32)。徐佳丽等以丙烯酸、顺丁烯二酸酐、衣康酸为单体,通过自由基聚合制备聚羧酸型助剂,铬鞣后裸皮对铬的吸收率为92%,废液中Cr2O3的含量为350mg/L。(徐佳丽,罗建勋.一种聚羧酸型助剂的合成与应用研究[J].中国皮革,2017,46(03):35-41)。姚棋等将端羧基超支化聚合物(HBPC)高吸收铬助剂应用于浸酸猪皮以及白皮粉的鞣制中,3%HBPC能够使铬的吸收率达95.2%,比常规铬鞣法提高了49.9%(姚棋,李征,王朝影,等.超支化聚合物作为高吸收铬鞣助剂的应用[J].中国皮革,2019,48(03):14-20)。
但以上高吸收铬鞣方法存在成本高、工艺复杂,铬吸收率约在80-95%,成革性能不能达到要求等问题。
本发明提出一种含酮磺酸根结构的高吸收铬鞣助剂的制备方法及高吸收铬鞣应用,助剂中引入酮羰基和磺酸根结构,能实现胶原的多点位改性,增加胶原中与三价铬配位位点,增加皮革中三价铬的结合量,实现铬鞣剂的高吸收,减少废液中铬的排放。
发明内容
发明目的:本发明的第一目的为提供一种含酮磺酸根结构的高吸收铬鞣助剂,本发明的第二目的为提供该含酮磺酸根结构的高吸收铬鞣助剂的制备方法,本发明的第三目的为提供该含酮磺酸根结构的高吸收铬鞣助剂在皮革浸酸工序及铬鞣工序中的应用。
技术方案:本发明的含酮磺酸根结构的高吸收铬鞣助剂,助剂的分子结构如下:
其中R1=三氟甲基(-CF3)、甲基(-CH3)、乙酰亚甲基(CH3COCH2-)、苯甲酰亚甲基(C6H5COCH2-)。
本发明的含酮磺酸根结构的高吸收铬鞣助剂的制备方法:以含酮羰基的咪唑衍生物及磺酸内酯为原料,在低极性非质子有机溶剂中,30-90℃反应4-12h,制备含酮磺酸根结构的高吸收铬鞣助剂。
所述的含酮羰基的咪唑衍生物为1-乙酰基咪唑(CAS登录号2466-76-4)、1-(三氟乙酰基)咪唑(CAS登录号1546-79-8)、1-(三氯乙酰基)咪唑(CAS登录号56739-51-6)、1-(1,3-丁二酮)-咪唑(CAS登录号487060-63-9)、1-咪唑-3-苯基-1,3-丙二酮(CAS登录号1787795-00-9)的一种;所述的磺酸内酯为1,3-丙烷磺酸内酯或1,4-丁烷磺酸内酯。
所述的低极性非质子有机溶剂为正己烷、环己烷、石油醚、二氯甲烷、1,4-二氧六环等,于30-90℃反应4-12h。
所述的含乙酰基咪唑衍生物与磺酸内酯的摩尔配比为1∶(0.98-1.02)。
进一步地,本发明所述的含酮磺酸根结构的高吸收铬鞣助剂在皮革浸酸工序及铬鞣工序中的应用:应用于高吸收铬鞣工艺:加入灰皮质量1.2-2.5%的高吸收铬鞣助剂,转动30-60分钟,浴液的pH值调节至2.5-3.2;加入灰皮质量3.5%-4.5%的碱度33.3%铬粉,温度20℃-25℃,转动2-4h;然后分4次加入灰皮质量1.5%-2.2%的小苏打水溶液(浓度为10%),每次间隔20min,调节pH至3.8-4.2,转动60min,补充灰皮质量150%的40℃热水,转动2h,停鼓过夜,次日转30min,出鼓搭马静置,得到蓝湿革,蓝湿革耐沸水煮,颜色纯正,粒面细致,革身柔软。
有益效果:与现有技术相比,本发明具有如下显著优点:
(1)本发明含有1-2个酮羰基,能够与皮胶原蛋白中的氨基反应,引入磺酸根,增加了三价铬的配位点位;
(2)本发明所述的含酮磺酸根结构的高吸收铬鞣助剂,其制备步骤简单,所得化合物官能度高;
(3)磺酸根能够与铬形成稳定配位,显著提高皮胶原与三价铬的配位位点,起到高吸收铬鞣的作用;
(4)不改变传统制革工艺的步骤,只需在浸酸工序及铬鞣工序中加入助剂即可。
说明书附图
图1含酮磺酸根结构的高吸收铬鞣助剂的结构示意图
图2 1-乙酰基-3-(丙基-3-磺酸基)咪唑核磁氢谱
具体实施方式
下面结合实施例对本发明做进一步的详细描述,但发明的实施方案不局限于此。
实施例1
1-乙酰基-3-(丙基-3-磺酸基)咪唑的合成
在100mL四口烧瓶中加入二氯甲烷60mL,加入0.03moL 1-乙酰基咪唑和0.03moL丙烷磺酸内酯,搅拌,回流反应4h,冷却过滤得到白色固体,即为产物,核磁氢谱确证结构;产物结构式如下:
1-乙酰基-3-(丙基-3-磺酸基)咪唑的核磁氢谱(D2O-d2):
8.66ppm(s,1H,-NCHN-),7.45ppm(d,1H,-NCHCHN-),7.37ppm(d,1H,-NCHCHN-),4.30ppm(t,2H,-NCH2CH2CH2SO3),2.82ppm(t,2H,-NCH2CH2CH2SO3),2.23ppm(m,2H,-NCH2CH2CH2SO3),1.94ppm(s,3H,CH3CO-).
将本发明含酮磺酸根结构的高吸收铬鞣助剂应用于黄牛皮的浸酸、铬鞣过程,测试坯革的收缩温度;测定铬鞣废液中及铬鞣坯革中三价铬的含量,并换算成三氧化二铬的含量。应用性能如表2,实施例1的高吸收铬鞣助剂,坯革收缩温度为102.5℃,铬鞣废液中及铬鞣坯革中三价铬分别是3.78g/L和237.6mg/L,铬鞣剂的吸收率达94.5%。
实施例2
1-乙酰基-3-(丁基-4-磺酸基)咪唑的合成
在100mL四口烧瓶中加入正己烷60mL,加入0.03moL 1-乙酰基咪唑和0.032moL丁烷磺酸内酯,搅拌,回流反应8h,过滤得到白色固体,即为产物,核磁氢谱确证结构;产物结构式如下:
1-乙酰基-3-(丁基-4-磺酸基)咪唑的核磁氢谱(D2O-d2):
8.66ppm(s,1H,-NCHN-),7.45ppm(d,1H,-NCHCHN-),7.37ppm(d,1H,-NCHCHN-),4.30ppm(t,2H,-NCH2CH2CH2CH2SO3),2.82ppm(t,2H,-NCH2CH2CH2CH2SO3),2.24ppm(m,2H,-NCH2CH2CH2CH2SO3),2.13ppm(m,2H,-NCH2CH2CH2CH2SO3),1.97ppm(s,3H,CH3CO-).
将本发明含酮磺酸根结构的高吸收铬鞣助剂应用于黄牛皮的浸酸、铬鞣过程,测试坯革的收缩温度;测定铬鞣废液中及铬鞣坯革中三价铬的含量,并换算成三氧化二铬的含量。应用性能如表2,实施例2的高吸收铬鞣助剂,坯革收缩温度为101.9℃,铬鞣废液中及铬鞣坯革中三价铬分别是3.56g/L和466.5mg/L,铬鞣剂的吸收率达89.0%。
实施例3
1-三氟乙酰基-3-(丙基-3-磺酸基)咪唑的合成
在100mL四口烧瓶中加入二氯甲烷60mL,加入0.03moL 1-三氟乙酰基咪唑和0.032moL丙烷磺酸内酯,搅拌,回流反应4h,过滤得到白色固体,即为产物,核磁氢谱确证结构;产物结构式如下:
1-三氟乙酰基-3-(丙基-3-磺酸基)咪唑的核磁氢谱(D2O-d2):
8.72ppm(s,1H,-NCHN-),7.51ppm(d,1H,-NCHCHN-),7.42ppm(d,1H,-NCHCHN-),4.31ppm(t,2H,-NCH2CH2CH2SO3),2.82ppm(t,2H,-NCH2CH2CH2SO3),2.24ppm(m,2H,-NCH2CH2CH2SO3).
将本发明含酮磺酸根结构的高吸收铬鞣助剂应用于黄牛皮的浸酸、铬鞣过程,测试坯革的收缩温度;测定铬鞣废液中及铬鞣坯革中三价铬的含量,并换算成三氧化二铬的含量。应用性能如表2,实施例3的高吸收铬鞣助剂,坯革收缩温度为105.7℃,铬鞣废液中及铬鞣坯革中三价铬分别是3.86g/L和167.8mg/L,铬鞣剂的吸收率达96.5%。
实施例4
1-三氟乙酰基-3-(丁基-4-磺酸基)咪唑的合成
在100mL四口烧瓶中加入环己烷60mL,加入0.03moL 1-三氟乙酰基咪唑和0.032moL丁烷磺酸内酯,搅拌,回流反应4h,过滤得到白色固体,即为产物,核磁氢谱确证结构;产物结构式如下:
1-三氟乙酰基-3-(丁基-4-磺酸基)咪唑的核磁氢谱(D2O-d2):
8.86ppm(s,1H,-NCHN-),7.69ppm(d,1H,-NCHCHN-),7.46ppm(d,1H,-NCHCHN-),4.27ppm(t,2H,-NCH2CH2CH2CH2SO3),3.52ppm(t,2H,-NCH2CH2CH2CH2SO3),2.28ppm(m,2H,-NCH2CH2CH2CH2SO3),2.13ppm(m,2H,-NCH2CH2CH2CH2SO3).
将本发明含酮磺酸根结构的高吸收铬鞣助剂应用于黄牛皮的浸酸、铬鞣过程,测试坯革的收缩温度;测定铬鞣废液中及铬鞣坯革中三价铬的含量,并换算成三氧化二铬的含量。应用性能如表2,实施例4的高吸收铬鞣助剂,坯革收缩温度为104.6℃,铬鞣废液中及铬鞣坯革中三价铬分别是3.80g/L和218.2mg/L,铬鞣剂的吸收率达95.0%。
实施例5
1-(1,3-丁二酮)-3-(丙基-3-磺酸基)咪唑的合成
在100mL四口烧瓶中加入二氯甲烷50mL,加入0.03moL 1-(1,3-丁二酮)-咪唑和0.03moL丙烷磺酸内酯,搅拌,回流反应3h,冷却过滤得到白色固体,即为产物,核磁氢谱确证结构;产物结构式如下:
1-(1,3-丁二酮)-3-(丙基-3-磺酸基)咪唑的核磁氢谱(D2O-d2):
8.75ppm(s,1H,-NCHN-),7.53ppm(d,1H,-NCHCHN-),7.42ppm(d,1H,-NCHCHN-),4.23ppm(t,2H,-NCH2CH2CH2SO3),4.11ppm(s,2H,CH3COCH2CO-),2.82ppm(t,2H,-NCH2CH2CH2SO3),2.24ppm(m,2H,-NCH2CH2CH2SO3),2.07ppm(s,3H,CH3COCH2CO-).
将本发明含酮磺酸根结构的高吸收铬鞣助剂应用于黄牛皮的浸酸、铬鞣过程,测试坯革的收缩温度;利用ICP-AES测定铬鞣废液中及铬鞣坯革中三价铬的含量,并换算成三氧化二铬的含量。应用性能如表2,实施例5的高吸收铬鞣助剂,坯革收缩温度为106.4℃,铬鞣废液中及铬鞣坯革中三价铬分别是3.92g/L和104.3mg/L,铬鞣剂的吸收率达98.0%。
表1含酮磺酸根结构的高吸收铬鞣助剂的制备实例
原料1 | 原料2 | 收率(%) | |
实施例1 | 1-乙酰基咪唑 | 丙烷磺酸内酯 | 96% |
实施例2 | 1-乙酰基咪唑 | 丁烷磺酸内酯 | 92% |
实施例3 | 1-三氟乙酰基咪唑 | 丙烷磺酸内酯 | 98% |
实施例4 | 1-三氟乙酰基咪唑 | 丁烷磺酸内酯 | 95% |
实施例5 | 1-(1,3-丁二酮)-咪唑 | 丙烷磺酸内酯 | 97% |
表2铬含量及坯革性能测试
高吸收铬鞣助剂 | 收缩温度(℃) | 坯革铬含量(g/L) | 废液铬含量(mg/L) |
实施例1 | 102.5 | 3.78 | 237.6 |
实施例2 | 101.9 | 3.56 | 466.5 |
实施例3 | 105.7 | 3.86 | 167.8 |
实施例4 | 104.6 | 3.80 | 218.2 |
实施例5 | 106.4 | 3.92 | 104.3 |
Claims (4)
2.根据权利要求1所述的一种含酮磺酸根结构的高吸收铬鞣助剂的制备方法,其特征在于:所述的低极性非质子有机溶剂为正己烷、环己烷、石油醚、二氯甲烷或1,4-二氧六环,于30-90℃反应4-12h。
3.根据权利要求1所述的一种含酮磺酸根结构的高吸收铬鞣助剂的制备方法,其特征在于:含酮羰基的咪唑衍生物与磺酸内酯的摩尔配比为1∶(0.98-1.02)。
4.一种通过权利要求1所述的含酮磺酸根结构的高吸收铬鞣助剂制备方法获得的高吸收铬鞣助剂在皮革浸酸工序及铬鞣工序中的应用,其特征在于:应用于高吸收铬鞣工艺:加入灰皮质量1.2-2.5%的高吸收铬鞣助剂,转动30-60分钟,浴液的pH值调节至2.5-3.2;加入灰皮质量3.5%-4.5%的碱度33.3%铬粉,温度20℃-25℃,转动2-4h;然后分4次加入灰皮质量1.5%-2.2%的小苏打水溶液,浓度为10%,每次间隔20min,调节pH至3.8-4.2,转动60min,补充灰皮质量150%的40℃热水,转动2h,停鼓过夜,次日转30min,出鼓搭马静置,得到蓝湿革,蓝湿革耐沸水煮,颜色纯正,粒面细致,革身柔软。
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