Preparation of Magnesium Aluminum-Type Hydrotalcite Compounds Intercalated with Phosphorus Flame Retardants and Their Flame Retardant Application in Thermoplastic Polyurethane

doi:10.19894/j.issn.1000-0518.230044

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (9): 1288-1301.DOI: 10.19894/j.issn.1000-0518.230044

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Preparation of Magnesium Aluminum-Type Hydrotalcite Compounds Intercalated with Phosphorus Flame Retardants and Their Flame Retardant Application in Thermoplastic Polyurethane

Jun-Jie SHI, Zhe-Hang SHI, Hong-Zhou LI()

College of Environmental and Resources，College of Carbon Neutral Modern Industry，Engineering Research Center of Polymer Resources Green Recycling of Ministry of Education，Fujian Normal University，Fuzhou 350007，China

Received:2023-03-01 Accepted:2023-07-08 Published:2023-09-01 Online:2023-09-14
Contact: Hong-Zhou LI
About author:lihongzhou@fjnu.edu.cn
Supported by:
the National Natural Science Foundation of China(51903049);the Natural Science Foundation of Fujian Province(2021J01198);the Scientific and Technological Project of Quanzhou(2022C008R)

Abstract

Abstract:

Three phosphorus flame retardants 9，10-dihydro-9-oxa-10-phosphafi-10-oxide （DOPO）， ammonium polyphosphate （APP） and melamine polyphosphate （MPP） are intercalated into magnesium-aluminium type hydrotalcite （MAH） sheets by direct solvent-free preparation method， and three MAH compounds containing phosphorus flame retardants （DOPO-MAH， APP-MAH and MPP-MAH） are obtained. The three MAH compounds are added into thermoplastic polyurethane （TPU） to obtain their composites by hot-pressing. The compounds are characterized by X-ray diffraction， scanning electron microscopy， thermogravimetric analysis， and their composites are characterized via cone calorimetry. The results show that the dispersion of MPP in MAH is poor； the dispersion of DOPO and APP in MAH is better and the distribution of elemental phosphorus is uniform. The initial interlayer spacing of MAH is 4.11 nm. Both APP and MPP are intercalated at 0.5 h， and the final interlayer spacing is reduced to 3.93 and 4.04 nm， respectively. DOPO is completed after 0.5 h， and the interlayer spacing of the intercalated MAH is smaller， 3.86 nm. Compared with composites made from physical mixtures， the peak heat release rate of （DOPO-MAH-6h）/TPU and （APP-MAH-6h）/TPU is decreased from 669.3 kW/m² to 573.9 kW/m² and from 657.7 kW/m² to 405.9 kW/m². （MPP-MAH-6h）/TPU have no difference with （MPP+MAH）/TPU in peak heat release rate. Compared to the peak heat release rate of TPU， 1236.6 kW/m²， the peak heat release rate of （DOPO-MAH-6h）/TPU，（APP-MAH-6h）/TPU and （MPP-MAH-6h）/TPU was reduced by 53%， 67% and 57%， respectively. The results indicate that DOPO-MAH， APP-MAH and MPP-MAH can be used to improve the flame retardant properties of TPU， however， DOPO-MAH and APP-MAH have better prospects for flame retardant applications in TPU.

Key words: 9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Ammonium polyphosphate, Melamine pyrophosphate, Hydrotalcite intercalation, Thermoplastic polyurethane, Flame retardancy

CLC Number:

O629

Jun-Jie SHI, Zhe-Hang SHI, Hong-Zhou LI. Preparation of Magnesium Aluminum-Type Hydrotalcite Compounds Intercalated with Phosphorus Flame Retardants and Their Flame Retardant Application in Thermoplastic Polyurethane[J]. Chinese Journal of Applied Chemistry, 2023, 40(9): 1288-1301.

Figures/Tables 16

Fig.1 FT-IR curves of DOPO5-MAH1 （A）， APP5-MAH1 （B） and MPP5-MAH1 （C） compounds over time and corresponding ultrasonic preparation compounds

Fig.2 XRD comparison of DOPO5-MAH1 （A）， APP5-MAH1 （B） and MPP5-MAH1 （C） compounds and mixtures

Fig.3 XRD patterns of formation process of DOPO5-MAH1 （A）， APP5-MAH1 （B） and MPP5-MAH1 （C） compounds

Fig.4 SEM images and the corresponding EDS mapping images of MAH （A）， DOPO5-MAH1-6h （B）， APP5-MAH1-6h （C） and MPP5-MAH1-6h （D） compounds

Fig.5 TG （A） and DTG （B） curves of DOPO5-MAH1 compounds and mixtures

Table 1 Thermogravimetric parameters of DOPO5-MAH1 compounds and mixtures

Sample	T_5%/℃	T_10%/℃	Maximum thermal mass loss temperature/℃	Mass residue ratio/% at 800 ℃
DOPO	221.4	237.0	303.0	0
MAH	170.1	206.8	215.3	57.8
DOPO5+MAH1	176.5	207.7	214.8	47.8
DOPO5-MAH1-6h	191.4	209.9	203.0	55.3

Fig.6 TG （A） and DTG （B） curves of APP5-MAH1 compounds and mixtures

Table 2 Thermogravimetric parameters of APP5-MAH1 compounds and mixtures

Sample	T_5%/℃	T_10%/℃	Maximum thermal mass loss temperature/℃	Mass residue ratio/% at 800 ℃
APP	296.2	324.9	578.7	44.1
MAH	170.1	206.8	215.3	57.8
APP5+MAH1	176.8	209.1	349.4	56.6
APP5-MAH1-6h	259.3	301.8	319.3	64.6

Fig.7 TG （A） and DTG （B） curves of MPP5-MAH1 compounds and mixtures

Table 3 Thermogravimetric parameters of MPP5-MAH1 compounds and mixtures

Sample	T_5%/℃	T_10%/℃	Maximum thermal mass loss temperature/℃	Mass residue ratio/% at 800 ℃
MPP	241.2	275.4	390.5	30.2
MAH	171.5	206.8	215.0	57.8
MPP5+MAH1	110.6	232.6	299.7	35.2
MPP5-MAH1-6h	207.5	264.2	402.1	33.4

Fig.8 Cone calorimeter tests of TPU， DOPO-MAH compounds and composites： HRR （A）， THR （B） and SPR （C）

Table 4 Cone test data of TPU and DOPO-MAH

Sample	TTI/s	Peak-HRR/（kW·m^-2）	THR/（MJ·m^-2）	SPR/（m²·s^-1）	MLR/（g·s^-1）
TPU	22	1 236.6	105.7	0.19	0.36
MAH/TPU	35	679.7	97.0	0.11	0.23
DOPO/TPU	36	1 214.5	102.1	0.24	0.29
（DOPO+MAH）/TPU	40	669.3	103.4	0.13	0.22
（DOPO-MAH-6h）/TPU	45	573.9	98.2	0.13	0.20

Fig.9 Cone calorimeter tests of TPU， APP-MAH compounds and composites： HRR （A）， THR （B） and SPR （C）

Table 5 Cone test data of TPU and APP-MAH

Sample	TTI/s	Peak-HRR/（kW·m^-2）	THR/（MJ·m^-2）	SPR/（m²·s^-1）	MLR/（g·s^-1）
TPU	22	1 236.6	105.7	0.19	0.36
MAH/TPU	35	679.7	97.0	0.11	0.23
APP/TPU	32	963.0	96.7	0.16	0.31
（APP+MAH）/TPU	33	657.7	89.1	0.12	0.25
（APP-MAH-6h）/TPU	36	405.9	71.2	0.09	0.14

Fig.10 Cone calorimeter tests of TPU， MPP-MAH compounds and composites： HRR （A）， THR （B） and SPR （C）

Table 6 Cone test data of TPU and MPP-MAH

Sample	TTI/s	Peak-HRR/（kW·m^-2）	THR/（MJ·m^-2）	SPR/（m²·s^-1）	MLR/（g·s^-1）
TPU	22	1 236.6	105.7	0.19	0.36
MAH/TPU	35	679.7	97.0	0.11	0.23
MPP/TPU	30	744.3	99.5	0.12	0.26
（MPP+MAH）/TPU	32	513.7	94.4	0.11	0.19
（MPP-MAH-6h）/TPU	40	524.0	91.3	0.10	0.18

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Preparation of Magnesium Aluminum-Type Hydrotalcite Compounds Intercalated with Phosphorus Flame Retardants and Their Flame Retardant Application in Thermoplastic Polyurethane

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