纤维素基共聚型聚羧酸减水剂的合成及其性能

doi:10.16085/j.issn.1000-6613.2024-0139

摘要/Abstract

摘要：

以天然纤维为原料，采用接枝醚化-烯丙基氯双键改性-水溶液自由聚合路线制备纤维素基共聚型聚羧酸减水剂（HEPCEs），通过傅里叶变换红外光谱、凝胶渗透色谱对产品HEPCEs进行分子结构分析，通过净浆流动度、经时变化流动度测试对HEPCEs减水性能进行评价，并同时进行了分子粒径、zeta电位以及吸附层厚度的测试，探究HEPCEs对水泥净浆的作用机理。结果表明，纤维素基共聚型聚羧酸减水剂中改性纤维素聚醚（DBHECs）适宜替代量为5%~10%，过多替代会出现支链缠绕并阻碍羧酸基团锚固，适量替代的纤维素结构引入可以在保持较好吸附性能的同时进一步提升减水剂的性能，超过商用高效减水剂标准，并表现出一定的缓释作用。

关键词: 纤维素聚醚, 改性, 生物基, 聚羧酸减水剂, 自由基共聚

Abstract:

The cellulose based copolymer polycarboxylic acid water reducer (HEPCEs) was prepared from natural fiber by grafting etherification, nucleophilic substitution and free polymerization. The molecular structure of synthetic HEPCEs was analyzed by infrared spectrum and gel permeation chromatography. The performance of HEPCEs was tested from the aspects of paste fluidity and time varying fluidity. The mechanism of action of HEPCEs on cement slurry by testing molecular particle size, zeta potential and adsorption layer thickness was further investigated. The results showed that the suitable substitution amount of modified cellulose polyether DBHECs in HEPCEs was 5%—10%. Excessive substitution of DBHECs would lead to branch chain entanglement and hindering the anchoring of carboxylic acid groups, causing a decrease in the performance of the water reducing agent. The introduction of appropriate substitution of cellulose structure can effectively further improve the performance of water reducing agents while maintaining good adsorption performance. From experiments with time variation, HEPCEs-5 indicated good performance and exhibited a certain degree of sustained release effect.

Key words: cellulose polyether, modified, bio-based, polycarboxylate water reducing agent, free radical copolymerization

中图分类号:

TU528.042.2

陈慕华, 嵇震, 王芳, 黄凯健, 付博, 刘博, 刘绍忠, 朱新宝. 纤维素基共聚型聚羧酸减水剂的合成及其性能[J]. 化工进展, 2024, 43(S1): 564-570.

CHEN Muhua, JI Zhen, WANG Fang, HUANG Kaijian, FU Bo, LIU Bo, LIU Shaozhong, ZHU Xinbao. Synthesis and properties of cellulose based copolymer polycarboxylate superplasticizer[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 564-570.

图/表 11

参考文献 23

1	ZHI Zhenzhen, MA Baoguo, JIAN Shouwei, et al. Thermal analyses: Effect of cellulose ethers on hydration of high-strength gypsum[J]. Journal of Thermal Analysis and Calorimetry, 2017, 129: 1547-1554.
2	黄凤远. 天然高分子基混凝土减水剂合成与应用[D]. 大连: 大连理工大学, 2008.
	HUANG Fengyuan. Synthesis and application of concrete water reducers based on natural polymers[D]. Dalian: Dalian University of Technology, 2008.
3	KUMAR Mukesh, SINGH N P, SINGH N B. Effect of water proofing admixture on the hydration of Portland cement[J]. Indian Journal of Chemical Technology, 2009, 16(6): 499-506.
4	苗方利, 姚治会, 张鼎. 淀粉基减水剂对水泥及混凝土性能的影响[J]. 硅酸盐通报, 2021, 40(3): 758-764.
	MIAO Fangli, YAO Zhihui, ZHANG Ding. Effect of starch-based water reducer on properties of cement and concrete[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(3): 758-764.
5	ZHONG Dingming, LIU Qiandi, ZHENG Dafeng. Synthesis of lignin-grafted polycarboxylate superplasticizer and the dispersion performance in the cement paste[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 642: 128689.
6	钟定明. 木质素与聚羧酸的协同性及木质素接枝聚羧酸减水剂的合成研究[D]. 广州: 华南理工大学, 2021.
	ZHONG Dingming. Synergism between lignin and polycarboxylate and synthesis of lignin grafting polycarboxylate water reducer[D]. Guangzhou: South China University of Technology, 2021.
7	付新建, 张战营, 朱孔赞, 等. 羟丙基纤维素改性聚羧酸减水剂的合成及性能研究[J]. 混凝土, 2014(11): 111-114.
	FU Xinjian, ZHANG Zhanying, ZHU Kongzan, et al. Synthesis of polycarboxylate type superplasticizer modified by hydroxypropyl cellulose[J]. Concrete, 2014(11): 111-114.
8	BIAN Hang, ZHANG Xuejian, LI Yongtao, et al. Comparison of casein and polycarboxylate modified cellulose nanocrystals as superplasticizers in self-leveling mortars[J]. Science of Advanced Materials, 2022, 14(11): 1710-1715.
9	TAN Hongbo, ZOU Fubing, MA Baoguo, et al. Effect of sodium tripolyphosphate on adsorbing behavior of polycarboxylate superplasticizer[J]. Construction and Building Materials, 2016, 126: 617-623.
10	郑大锋, 邱学青, 楼宏铭. XPS测定减水剂吸附层厚度[J]. 化工学报, 2008, 59(1): 256-259.
	ZHENG Dafeng, QIU Xueqing, LOU Hongming. Measurement of adsorption layer thickness of water reducer by using XPS[J]. CIESC Journal, 2008, 59(1): 256-259.
11	ESKANDARI Mohammad, NAJDIAN Atena, SOLEYMAN Rouhollah. Investigation on the interactions between fullerene and β -CD-g-hyperbranched polyglycerol to produce water-soluble fullerene[J]. Chemical Physics, 2016, 472: 9-17.
12	XIA Keqiang, OUYANG Qin, CHEN Yousi, et al. Preparation and characterization of lignosulfonate-acrylonitrile copolymer as a novel carbon fiber precursor[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(1): 159-168.
13	LIU Xiaohuan, WANG Jifu, YU Juan, et al. Preparation and characterization of lignin based macromonomer and its copolymers with butyl methacrylate[J]. International Journal of Biological Macromolecules, 2013, 60: 309-315.
14	孙良. 聚羧酸系减水剂的常温合成及性能研究[D]. 郑州: 郑州大学, 2018.
	SUN Liang. Study on the synthesis and properties of polycarboxylic acid water reducer at room temperature[D]. Zhengzhou: Zhengzhou University, 2018.
15	白武东. 聚羧酸系高性能减水剂合成工艺与性能研究[D]. 太原: 中北大学, 2021.
	BAI Wudong. Preparation technology and performance study of polycarboxylate superplasticizer[D]. Taiyuan: North University of China, 2021.
16	SHU Xin, RAN Qianping, LIU Jiaping, et al. Tailoring the solution conformation of polycarboxylate superplasticizer toward the improvement of dispersing performance in cement paste[J]. Construction and Building Materials, 2016, 116: 289-298.
17	曹恩祥. 聚羧酸减水剂对水泥净浆体系流变性能的作用机理研究[D]. 北京: 清华大学, 2011.
	CAO Enxiang. Research on mechanism of polycarboxylate superplasticizer on rheological properties of cement paste[D]. Beijing: Tsinghua University, 2011.
18	王栋民, 张川川, 张力冉, 等. 马来酸酐聚羧酸减水剂的合成、表征与缓释机理[J]. 化工进展, 2018, 37(8): 3045-3050.
	WANG Dongmin, ZHANG Chuanchuan, ZHANG Liran, et al. Synthesis, characterization and slow-release mechanism of maleic anhydride polycarboxylate-type superplasticizers[J]. Chemical Industry and Engineering Progress, 2018, 37(8): 3045-3050.
19	MA Yihan, SHA Shengnan, ZHOU Beibei, et al. Adsorption and dispersion capability of polycarboxylate-based superplasticizers: A review[J]. Journal of Sustainable Cement-Based Materials, 2022, 11(5): 319-344.
20	SHA Shengnan, WANG Min, SHI Caijun, et al. Influence of the structures of polycarboxylate superplasticizer on its performance in cement-based materials—A review[J]. Construction and Building Materials, 2020, 233: 117257.
21	KARAKUZU Kemal, KOBYA Veysel, Ali MARDANI-AGHABAGLOU, et al. Adsorption properties of polycarboxylate ether-based high range water reducing admixture on cementitious systems: A review[J]. Construction and Building Materials, 2021, 312: 125366.
22	ZHANG Yanrong, KONG Xiangming, LU Zhenbao, et al. Effects of the charge characteristics of polycarboxylate superplasticizers on the adsorption and the retardation in cement pastes[J]. Cement and Concrete Research, 2015, 67: 184-196.
23	PLANK Johann, HIRSCH Christian. Impact of zeta potential of early cement hydration phases on superplasticizer adsorption[J]. Cement and Concrete Research, 2007, 37(4): 537-542.

样品	数均分子量	重均分子量	PDI	粒径/nm
HPCEs	58811	69898	1.18	12.38
HEPCEs-5	60976	77687	1.27	20.50
HEPCEs-10	62765	84100	1.33	20.92
HEPCEs-15	61951	86195	1.39	34.69

样品	数均分子量	重均分子量	PDI	粒径/nm
HPCEs	58811	69898	1.18	12.38
HEPCEs-5	60976	77687	1.27	20.50
HEPCEs-10	62765	84100	1.33	20.92
HEPCEs-15	61951	86195	1.39	34.69

样品	固含量	0.3%掺量		0.6%掺量		0.9%掺量
样品	固含量	净浆流动度/mm	净浆减水率/%	净浆流动度/mm	净浆减水率/%	净浆流动度/mm	净浆减水率/%
HPCEs	40.20%	273.5	60.5	296.0	64.5	280.0	62.2
HEPCEs-5	39.70%	258.7	58.6	295.0	64.5	305.0	65.2
HEPCEs-10	39.30%	176.3	47.3	295.0	64.5	304.3	65.2
HEPCEs-15	39.80%	150.0	45.6	260.0	58.6	302.5	65.0

样品	固含量	0.3%掺量		0.6%掺量		0.9%掺量
样品	固含量	净浆流动度/mm	净浆减水率/%	净浆流动度/mm	净浆减水率/%	净浆流动度/mm	净浆减水率/%
HPCEs	40.20%	273.5	60.5	296.0	64.5	280.0	62.2
HEPCEs-5	39.70%	258.7	58.6	295.0	64.5	305.0	65.2
HEPCEs-10	39.30%	176.3	47.3	295.0	64.5	304.3	65.2
HEPCEs-15	39.80%	150.0	45.6	260.0	58.6	302.5	65.0

样品	不同掺量下水泥净浆流动度/mm
样品	0.3%	0.6%	0.9%
HPCEs	170.0	307.5	320.0
HEPCEs-5	157.5	317.5	320.0
HEPCEs-10	—	308.7	325.0
HEPCEs-15	—	287.5	303.7