低浓度胍胶用协同型有机硼交联剂的制备及性能评价

doi:10.3969/j.issn.2097-2806.2026.09.007

Abstract

Abstract:

At present, the usage amount of guar gum in guar gum fracturing fluids is relatively high, and the existing organic boron crosslinkers are poor in controllability of crosslinking time and inadequate in temperature and shear resistance. To solve these problems, in this work, an organic boron crosslinker （BBS） suitable for low-concentration guar gum was synthesized by one-pot method under alkaline conditions by using borax, ethylene glycol, triethanolamine and glucose as raw materials. The synthesis conditions were optimized by single-factor and orthogonal experiments, and the product structure was characterized by FT-IR. The comprehensive performance of the crosslinked gel formed by BBS with 0.2% guar gum solution was evaluated and compared with that of a commercial crosslinker JL-9. The results showed that the optimized formulation （in mass fractions） of BBS was determined as 25.3% borax, 25.3% triethanolamine, 14.2% glucose, 19.7% ethylene glycol, 1.1% NaOH and 14.4% distilled water. Under the conditions of a reaction time of 4 h at 50 ℃, the apparent viscosity of the crosslinked gel reached 72 mPa·s. FT-IR analysis confirmed the formation of nitrogen-boron heterocyclic cage-like structure in the product. The BBS-crosslinked gel exhibited superior performance compared to JL-9 in delayed crosslinking, temperature and shear resistance, filtration loss control, and rapid gel breaking with low residue. At pH of 10 and the guar gum-to-crosslinker mass ratio of 100∶0.4, the crosslinking time was 264 s, and the gel viscosity reached 66 mPa·s. The synergistic effect of several borate esters in BBS enabled the stepwise release of active B （OH）₄^-, endowing the system with delayed crosslinking, viscosity maintenance, and high-temperature shear resistance, which demonstrated promising application prospects in deep and high-temperature fracturing operations.

Key words: low-concentration guar gum, organic boron crosslinker, fracturing fluid, synergistic crosslinking, structural characterization

CLC Number:

TE37

Shuai Wang, Zhongguo Ma, Junjie Li, Zhengfan Wang, Liaoliao Gao, Fangling Qin. Preparation and performance evaluation of synergistic organic boron crosslinker for low-concentration guar gum[J].China Surfactant Detergent & Cosmetics, 2026, 56(9): 1188-1197.

Figures/Tables 15

Tab.1

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Tab.2

Fig.7

Fig.8

Fig.9

Fig.10

Tab.3

Tab.4

Fig.11

References 28

[1]	Wang X Y, Song Y C, Wu P, et al. Rheological properties of hydroxypropyl guar gum fracturing fluids: Effects of cross-linking agents[J]. Carbohydrate Polymers, 2025, 366: 123837. doi: 10.1016/j.carbpol.2025.123837
[2]	Shao N, Yan Y S, Yu P Z, et al. Synthesis and performance evaluation of an organic boron crosslinker for low-concentration fracturing fluid[J]. Oilfield Chemistry, 2019, 36 (3) : 388-393.
[3]	Qin F L, Zhang B B, Wang Z F, et al. Synthesis and performance evaluation of organic boron crosslinker BOA for low-concentration guar gum fracturing fluid[J]. Applied Chemical Industry, 2017, 46(6) : 1055-1057.
[4]	Chen L J, Gong R P, Wang J, et al. Influence of reservoir physical properties on guar gum fracturing fluid damage in unconventional tight reservoirs[J]. Physics of Fluids, 2024, 36: 046608. doi: 10.1063/5.0203620
[5]	Xiong J J. Study on gel-breaking mechanism of guar gum fracturing fluid by biological enzyme/ammonium persulfate[J]. Petroleum Drilling Techniques, 2024, 52 (6) : 126-130.
[6]	Xu D, Zhu W P, Bai K S, et al. Research progress on synthesis of organic boron crosslinkers for guar gum fracturing fluid system[J]. Polymer Bulletin, 2023, 36 (2) : 245-249.
[7]	Zhang Z, Mao J, Zhang Y, et al. Improved fracturing fluid using organic amino boron composite crosslinker with B-N covalent bond[J]. J. Appl. Polym. Sci., 2019, 136 (25) : 47675.
[8]	Wang Y L, Zhang C B, Xu N, et al. Synthesis and properties of organoboron functionalized nanocellulose for crosslinking low polymer fracturing fluid system[J]. RSC Advances, 2021, 11 (22) : 13466-13474. doi: 10.1039/d0ra10105b pmid: 35423881
[9]	Xu D P, Zhao Z C, Ma F X, et al. Design of polymer boron crosslinking agents based on scale effects and study of the crosslinking mechanism of guar gum at ultra-low concentrations[J]. International Journal of Biological Macromolecules, 2026, 340 (1) : 150086.
[10]	Li Q, Wang F L, Wang Y L, et al. Influence of organoboron cross-linker and reservoir characteristics on filtration and reservoir residual of guar gum fracturing fluid in low-permeability shale gas reservoirs[J]. Environmental Science and Pollution Research, 2022, 29: 82975-82985. doi: 10.1007/s11356-022-21577-0
[11]	Wang Q D, Dong T F, Feng Q, et al. Synthesis and performance evaluation of polyamine boron crosslinker for gel fracturing fluid[J]. Gels, 2026, 12 (3) : 236.
[12]	Li X L, Ding L, Shi H Q, et al. Development of ultra-low concentration hydroxypropyl guar fracturing fluid system and its application in sulige gas field[J]. Chemical Engineering of Oil & Gas, 2013, 42(3) : 274-278.
[13]	Davidson B L, Manyin E, Morris N E, et al. Kinetic and thermodynamic investigation into the formation of diol-boric acid complexes using NMR and computational analysis[J]. ACS Omega, 2025, 10 (46) : 55824-55831. doi: 10.1021/acsomega.5c07314
[14]	Smoum R, Rubinstein A, Srebnik M. Combined ¹H, ¹³C and ¹¹B NMR and mass spectral assignments of boronate complexes of D- (+) -glucose, D- (+) -mannose, methyl-α-D-glucopyranoside, methyl-β-D-galactopyranoside and methyl-α-D-mannopyranoside[J]. Magnetic Resonance in Chemistry, 2003, 41: 1015-1020. doi: 10.1002/mrc.v41:12
[15]	Takahashi A, Yamanishi M, Kameyama A. Lewis Adduct-Dissociating hydrolysis of boratrane for Water-Triggered dehydration of copolymers with a hydrophobic moiety[J]. ACS Macro Letters, 2022, 11 (6) : 766-771. doi: 10.1021/acsmacrolett.2c00161 pmid: 35622979
[16]	Wang C X, Liang T T, Wei C Q. Synthesis and characterization of triethanolamine borate[J]. Advanced Materials Research, 2013, 709: 28-31. doi: 10.4028/www.scientific.net/AMR.709
[17]	Tang H B, Wang S B, Guo J C. Effect of pH value on performance of hydroxypropyl guar gum fracturing fluid[J]. Oilfield Chemistry, 2016, 33 (2) : 220-223.
[18]	Li J N, Li L H, Zhang J S, et al. Study of synthesis and properties of organic boron crosslinker[J]. Applied Chemical Industry, 2015, 44(1) : 122-124.
[19]	Wang Z F. Synthesis and performance evaluation of organic boron crosslinker for low-concentration guar gum fracturing fluid[D]. Xi'an: Xi'an Shiyou University, 2023.
[20]	Berionni G, Leonov A I, Mayer P, et al. fine-tuning the nucleophilic reactivities of boron ate complexes derived from aryl and heteroaryl boronic esters[J]. Angewandte Chemie International Edition, 2015, 54 (9) : 2780-2783. doi: 10.1002/anie.v54.9
[21]	Brooks W L A, Deng C C, Sumerlin B S. Structure-reactivity relationships in boronic acid-diol complexation[J]. ACS Omega, 2018, 3 (12) : 17863-17870. doi: 10.1021/acsomega.8b02999 pmid: 31458380
[22]	Pretesch E, Buhlmann P, Badertscher M. Spectral data tables -structural elucidation of organic compounds[M]. 4th ed. Beijing: Science Press, 2023: 269-335.
[23]	Luo P D, Song Z F, Zhang J B, et al. Preparation and performance evaluation of polyamino boron crosslinkers[J]. Fine Chemicals, 2019, 36 (9) : 1930-1935.
[24]	Cui J, Zhang R S, Zhao M Y, et al. Synthesis, characterization and performance pvaluation of novel organic boron crosslinkers for fracturing fluids[J]. Applied Chemical Industry, 2017, 46 (6) : 1055-1057.
[25]	Tang Y, Pang L B, Wang D P. Preparation and characterization of borate bioactive glass cross-linked PVA hydrogel[J]. Journal of Non-Crystalline Solids, 2017, 476: 25-29. doi: 10.1016/j.jnoncrysol.2017.07.017
[26]	Shen L, Huang W Z, Xiang L, et al. Synthesis and property study of crosslinker for ultrahigh temperature resistant guar gum fracturing fluid[J]. Chemical Engineering of Oil & Gas, 2017, 46 (3) : 80-84.
[27]	Takahashi A, Yamanishi M, Kameyama A. Reversible modulation of polymer chain mobility by selective cage opening and closing of pendant boratrane units[J]. Polymer Journal, 2025, 57 (3) : 259-268. doi: 10.1038/s41428-024-00986-7
[28]	He C Z, Dong J, Xu C R, et al. n-coordinated organoboron in polymer synthesis and material science[J]. Acs Polymers Au, 2023, 3 (1) : 5-27. doi: 10.1021/acspolymersau.2c00046

因素水平	w （NaOH） / %	w （硼砂） / %	w （三乙醇胺） / %	w （葡萄糖） / %
1	1.1	22.1	22.1	14.2
2	1.3	23.7	23.7	15.8
3	1.4	25.3	25.3	17.4

编号	w （NaOH） / %	w （硼砂） / %	w （三乙醇胺）/%	w （葡萄糖） /%	冻胶黏度/ （mPa·s）
1	1.1	22.1	22.1	14.2	90
2	1.1	23.7	23.7	15.8	75
3	1.1	25.3	25.3	17.4	87
4	1.3	22.1	23.7	17.4	63
5	1.3	23.7	25.3	14.2	90
6	1.3	25.3	22.1	15.8	87
7	1.4	22.1	25.3	15.8	78
8	1.4	23.7	22.1	17.4	66
9	1.4	25.3	23.7	14.2	78
均值K₁	84	77	81	86
均值K₂	80	77	72	80
均值K₃	74	84	85	72
极差R	10	7	13	14
排秩	3	4	2	1

交联剂种类	初滤失量/ （m³/m²）	造壁滤失系数/ （m/min^?）
BBS	1.42×10^-3	2.13×10^-4
JL-9	1.38×10^-3	2.77×10^-4

交联剂	不同时间冻胶的破胶状况						破胶液黏/ （mPa·s）	残渣含量/ （mg/L）
交联剂	10 min	20 min	30 min	60 min	90 min	120 min	破胶液黏/ （mPa·s）	残渣含量/ （mg/L）
JL-9	未破胶	未破胶	未破胶	黏度较大	轻微拉丝	完全破胶	2.83	92
BBS	未破胶	未破胶	拉丝	轻微拉丝	完全破胶	完全破胶	2.01	88

Preparation and performance evaluation of synergistic organic boron crosslinker for low-concentration guar gum

RichHTML

PDF (PC)

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 15

References 28

Related Articles 12

Metrics

Comments

Recommended 10

[1]	Bumin Guo, Jinwei Shen, Jian Zhao, Ling Chen, Yantao Xu, Yang Wang. Reservoir damage mechanism of the fracturing fluid based on a long-chain alkyl quaternary ammonium salt at different rock interfaces: Molecular dynamics simulation and experimental verification [J]. China Surfactant Detergent & Cosmetics, 2026, 56(9): 1158-1168.
[2]	Ruirui Guo, Haifeng Liu. Research on a novel supramolecular clean fracturing fluid suitable for deep coalbed methane wells [J]. China Surfactant Detergent & Cosmetics, 2026, 56(6): 739-746.
[3]	Haibing Cheng, Yong Zhang, Lei Sun, Weijia Li, Zhi Chen, Congming Tang, Li Chang. Synthesis and crosslinking properties of W-SN crosslinking agent [J]. China Surfactant Detergent & Cosmetics, 2025, 55(3): 279-285.
[4]	Jian Zhao, Bumin Guo, Jinwei Shen, Li Wang, Tianpeng Xu, Wenhui Bao. Study on the mechanism and kinetics of crosslinking in high-temperature-resistant seawater-based plant gum fracturing fluid [J]. China Surfactant Detergent & Cosmetics, 2025, 55(12): 1560-1566.
[5]	Jin Zhen, Zhang Chunsheng. Preparation and performance evaluation of organic zirconium gelled fracturing fluid with high temperature resistance and slowly-cross-linking [J]. China Surfactant Detergent & Cosmetics, 2023, 53(3): 279-284.
[6]	Yongkang Zhang, Mengmeng Liu, Zhiwei Wan, Yaocong Wang, Mimi Tian, Liewei Qiu. Effect of spacer on the performance of Gemini betaine surfactant in clean fracturing fluid [J]. China Surfactant Detergent & Cosmetics, 2023, 53(12): 1398-1404.
[7]	Zhong Ju, Sarsenbekuly Bauyrzhan, Yin Xia, Kang Wanli. Performance and application of high-temperature resistant carboxymethyl guar gum fracturing fluid [J]. China Surfactant Detergent & Cosmetics, 2023, 53(10): 1125-1131.
[8]	Yu Hongmei,Zhou Feng,Hua Ping,Li Jianhua,Qian Feng. Study on preparation method of magnetic carbon-based solid acid and its application in glycoside synthesis [J]. China Surfactant Detergent & Cosmetics, 2022, 52(7): 717-723.
[9]	Tang Yayuan,He Xuemei,Sun Jian,Wei Zhen,Li Changbao,Liu Guoming. Application and properties of the polysaccharide from red pulp pitaya stem in hand creams [J]. China Surfactant Detergent & Cosmetics, 2022, 52(4): 410-417.
[10]	CUI Xiu,FANG Bo,XU Hai-tao. Rheological properties of a novel clean fracturing fluid: the micellar system of 25-HP-21/NaSal [J]. China Surfactant Detergent & Cosmetics, 2020, 50(10): 653-659.
[11]	KANG Wan-li,LI Xin-xin,ZHAO Yi-lu,WANG Peng-xiang,HOU Xiao-yu,YANG Hong-bin. Construction of N-erucamido-N, N-dimethylamine and benzoic acid fracturing fluid system [J]. China Surfactant Detergent & Cosmetics, 2019, 49(9): 555-560.
[12]	LI Xia-qing, ZHANG Chi, ZHANG Gui-cai, GE Ji-jiang, WANG Zong-sheng. Applications of viscoelastic surfactant in oilfield [J]. China Surfactant Detergent & Cosmetics, 2014, 44(9): 521-524.