31P核磁共振波谱表征高聚合度聚磷酸铵及其链结构

doi:10.7503/cjcu20180019

摘要/Abstract

摘要：

以液体定量³¹P核磁共振波谱(³¹P NMR)为主要表征手段, 通过建立水中加盐促溶的高聚合度聚磷酸铵(APP)水溶液的制备方法, 研究不同溶解温度、测试温度及NMR参数等对APP聚合度的影响, 建立了³¹P NMR准确表征APP的聚合度及其链结构的方法. 研究结果表明, 于36 ℃在水中加盐溶解APP, 26 ℃下进行³¹P NMR测试, 既保证了APP溶液良好的溶解性, 又在水溶液制备和³¹P NMR测试过程中不引起APP降解, 测得的APP聚合度稳定、准确. 利用液体³¹P NMR确定了不同温度下APP盐水溶液中端基磷和中间磷弛豫时间(T₁), 发现T₁与温度呈线性关系, 弛豫时间参数(D₁)的设置影响APP聚合度结果, D₁设置不满足磷所需的T₁时, APP的聚合度结果偏大. ³¹P NMR表征APP链结构结果显示, APP的端基磷存在3种化学环境, 而溶液离子强度和温度会影响3种端基磷的化学位移; APP的中间磷中含有H⁺. 此外, 提出了中国化工行业标准HG/T 2770-2008中APP高聚合度测定存在的问题.

关键词: 聚磷酸铵, 聚合度, 链结构, 磷核磁共振, 弛豫时间

Abstract:

Ammonium polyphosphate(APP) of high polymerization degree is an kind of important inorganic polymer flame retardant. Characterization of APP with high polymerization degree and its solution property are a meaningful topic. In this paper, quantitative liquid ³¹P nuclear magnetic resonance(NMR) is used to characterize APP polymerization degree and chain structures. A method of preparing aqueous APP solution by adding NaCl in water to auxiliary dissolving was established without resulting in APP degradation. The effects of different dissolution and testing temperature, and different NMR parameters were studied on the characterization of APP polymerization degree. Finally, The method to accurately characterize the APP polymerization degree was suggested based on liquid ³¹P NMR, that is: dissolving APP could be in water at 36 ℃ with auxi-liary NaCl salt, setting the temperature as 26 ℃ in ³¹P NMR testing. In this case, the good solubility of APP could be achieved, at same time no degradation of APP happened, the measurement of APP polymerization degree can be stable and accurate. The relaxation time(T₁) of terminal phosphorus(P_end) and middle phosphorus(P_mid) at different temperatures were determined by liquid ³¹P NMR, and the relationship between T₁ and temperature was found to be linear. The relaxation time parameter(D₁) in ³¹P NMR has a great effect on the characterization of APP polymerization degree, and the polymerization degree of APP will be inaccurate when the setting of D₁ could not meet the T₁ required for phosphorus. Characterization of APP chain structures by ³¹P NMR showed that there are three kinds of chemical environments in the terminal phosphorus of APP, that is the P connecting with two N $H 4 +$ , one N $H 4 +$ and one H⁺, and two H⁺, respectively. The NaCl concentration and testing temperature obviously influence the chemical shift of terminal phosphorus in the three chemical environments. It was verified that there was the middle phosphorus connecting with H⁺ in APP as well.

Key words: Ammonium polyphosphate, Polymerization degree, Chain structure, ³¹P nuclear magnetic resonance(NMR), Relaxation time

中图分类号:

O631.6

TrendMD:

刘宜娜, 杨荣杰, 李定华, 梁嘉香, HU Weiguo. ³¹P核磁共振波谱表征高聚合度聚磷酸铵及其链结构. 高等学校化学学报, 2018, 39(9): 2080.

LIU Yina,YANG Rongjie,LI Dinghua,LIANG Jiaxiang,HU Weiguo. Characterization of High Polymerization Degree Ammonium Polyphosphate and Its Chain Structure by ³¹P NMR^†. Chem. J. Chinese Universities, 2018, 39(9): 2080.

图/表 18

Fig.1 31P NMR spectra of APP1# solution with 10 mg NaCl at 36 ℃(a) and NH4H2PO4(b)

Table 1 Characteristic phosphorous and polymerization degree(n) of APP1# at different testing conditions

Preparation conditon	Dissolving temperature/℃	Testing temperature/℃	P_free		P_end		P_mid		n
Preparation conditon	Dissolving temperature/℃	Testing temperature/℃	S_free	Ratio(%)	S_end	Ratio(%)	S_mid	Ratio(%)	n
NaCl auxiliary	26	26	6.69	0.64	2.62	0.25	1034.62	99.11	792
dissolving	36	26	6.77	0.61	2.46	0.22	1099.07	99.17	893
	36	36	6.92	0.66	2.71	0.26	1040.72	99.08	770
100 ℃ High temperature dissolving	100	26	7.21	7.20	3.83	3.82	989.34	98.89	519

Table 2 Polymerization degree of APP1# solution(10 mg NaCl) experiencing preservation for different time

Preservation temperature/℃	Polymerization degree, n
Preservation temperature/℃	2 h	5 h	8 h	11 h
26	792	782	764	754
36	770	773	513	460

Table 3 Repeatability of polymerization degree(n) of APP1# in 31P NMR tests

Testing number	n	Testing number	n
1	893	6	838
2	883	7	857
3	878	8	865
4	866	Average	865
5	840

Table 4 Characteristic phosphorus and polymerization degree of different APP samples with 10 mg NaCl auxiliary dissolving at 36 ℃

APP sample	S_free(%)	S_end(%)	S_mid(%)	n
5125#	0.52	0.17	98.64	1162
61231#	0.10	0.06	95.74	3193
714#	0.16	0.02	94.17	9419
715#	0.08	—	102.6	—

Fig.2 31P NMR spectra of 714#(a), 715#(b), 5125#(c) and 61231#(d) APP samples with 10 mg NaCl auxiliary dissolving at 36 ℃

Table 5 Characteristic phosphorus and polymerization degree of APP1# with 10 mg NaCl auxiliary dissolving at 36 ℃ at different relaxation time parameters

D₁/s	S_end	S_mid	n
1	1.68	957.85	1142
10	2.48	1058.56	855
20	2.54	1058.78	835
30	2.54	1058.77	835

Table 6 Relaxation time(T1) of phosphorus at different testing temperatures in 31P NMR for APP1# with 10 mg NaCl auxiliary dissolving at 36 ℃

Testing temperature/℃	T₁/s
Testing temperature/℃	P_free	P_end	P_mid
26	8.32	2.99	0.52
31	8.52	4.54	0.55
36	8.89	5.60	0.59
41	10.70	6.81	0.63
46	10.68	7.99	0.66
51	10.21	8.97	0.69
56	11.20	10.10	0.73

Fig.3 Relationship between temperature and relaxation time T1 of Pmid of APP1# with 10 mg NaCl auxiliary dissolving at 36 ℃

Fig.4 Phosphorous resonance peaks of APP1# with 10 mg NaCl auxiliary dissolving at 36 ℃ at different testing temperatures in 31P NMR (A) Pfree; (B) Pend; (C) Pmid. Temperature/℃: a. 26; b. 36; c. 46; d. 56.

Fig.5 Pend resonance peaks in three kinds of APP1# solutionsa. Ion exchange method; b. NaCl auxiliary dissolving at 36 ℃; c. dissolving at 100 ℃.

Table 7 Characteristic phosphorus in APP1# solution with acetic acid added

Acetic acid content(%)	P_freeratio(%)	P_end ratio(%)			Short chain P_midratio(%)	Long chain P_mid ratio(%)
Acetic acid content(%)	P_freeratio(%)	Peak 1	Peak 2	Peak 3	Short chain P_midratio(%)	Long chain P_mid ratio(%)
0	1.18	0.14	0.14	0.16	0.21	98.2
30	1.40	0.13	0.22	0.20	0.21	97.8
50	1.41	0.12	0.32	0.37	0.27	97.5

Fig.6 Pend resonance peaks in APP1# solutions with different acetic acid contentAcetic acid content(%): a. 0; b. 30; c. 50.

Fig.7 Pend structure of APP1# solution with 10 mg NaCl auxiliary dissolving at 36 ℃

Fig.8 Pend characteristics of of APP1# solutions with out NaCl dissolving at 100 ℃(a) and with 10 mg NaCl auxiliary dissolving at 36 ℃(b)

Fig.9 Pend characteristics of of APP1# solutions with different NaCl concentrationsNaCl concentration/(mg·mL-1): a. 0(100 ℃); b. 5; c. 10; d. 15; e. 20; f. 25.

Fig.10 Pend characteristics of APP1# solutions at different testing temperatures (A) NaCl auxiliary dissolving at 36 ℃; (B) high temperature dissolving at 100 ℃. Testing temperature/℃: a. 26; b. 31; c. 36; d. 41; e. 46; f. 51; g. 56.

Fig.11 Resonance peaks at different testing temperature of middle phosphorus Pmid in APP1# solution with 10 mg NaCl auxiliary dissolving at 36 ℃Testing temperature/℃: a. 26; b. 31; c. 36; d. 41; e. 46.

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³¹P核磁共振波谱表征高聚合度聚磷酸铵及其链结构

Characterization of High Polymerization Degree Ammonium Polyphosphate and Its Chain Structure by ³¹P NMR^†

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