羧酸金属盐β晶型成核剂合成及应用研究

doi:10.11949/j.issn.0438-1157.20190062

摘要/Abstract

摘要：

研究开发了一种新型的羧酸金属盐β晶型成核剂。此成核剂不仅高效诱导β-PP形成，而且成核效率高, β-成核PP的冲击强度可提高2~4倍，并且大幅提高PP热变形温度，有效缓解了聚丙烯制品的冲击强度和热变形温度二者之间的矛盾。目前已在PPR管材和PPH板材、大注件制品以及锂电池隔膜方面得到广泛的应用。

关键词: 聚丙烯, 羧酸金属盐, β晶成核剂

Abstract:

A new type of carboxylic acid metal salt β-crystalline nucleating agent is developed. It is a new compound. This nucleating agent not only efficiently induces the formation of β-PP, but also has a high nucleation efficiency. The impact strength of β-nucleating PP can be increased by 2 to 4 times, and the heat deformation temperature of PP can be greatly increased. The contradiction between the impact strength and the thermal deformation temperature of polypropylene products is effectively relieved. At present, it has been widely used in PPR tubes and PPH plates, large injection products, and lithium battery diaphragm.

Key words: polypropylene, carboxylate, β-nucleating agent

中图分类号:

TQ 325.14

赵文林, 何洁冰. 羧酸金属盐β晶型成核剂合成及应用研究[J]. 化工学报, 2019, 70(S1): 211-216.

Wenlin ZHAO, Jiebing HE. Synthesis and application of carboxylic acid metal salt beta crystal nucleating agent[J]. CIESC Journal, 2019, 70(S1): 211-216.

图/表 9

图1 羧酸金属盐NAB-81β晶型成核剂红外光谱图

Fig.1 IR spectra of NAB-81 β-crystalline nucleating agent

表1 PP经羧酸金属盐NAB-81β成核剂改性β晶型含量(DSC法)

Table 1 β-crystal content of PP modified by carboxylic acid metal salt NAB-81 β nucleating agent(DSC method)

β成核剂含量（质量分数）/%	T _β/℃	T _α/℃	ΔH _β/(J/g)	ΔH _α/ (J/g)	β晶含量K _β/%
0	—	164.22	—	65.23	—
0.01	152.71	168.30	55.54	6.61	89.82
0.02	152.72	168.58	54.57	5.25	91.61
0.05	152.41	168.27	68.48	6.06	92.23
0.15	152.71	168.05	82.82	7.55	92.01

图2 羧酸金属盐NAB-81β成核剂改性PP β晶型与α晶型DSC图

Fig.2 DSC of β-crystalline and α-crystalline of NAB-81 β-crystalline nucleating agent modified PP

图3 PP经0.01% NAB-81改性偏光显微镜图

Fig.3 Polarimetric of PP modified by 0.01% NAB-81

图4 PP经0.15% NAB-81改性偏光显微镜图

Fig.4 Polarimetric of PP modified by 0.15% NAB-81

图5 五次挤出β晶型与α晶型DSC图

Fig.5 DSC of β-crystal and α-crystal after extruded five times

表2 羧酸金属盐NAB-81不同浓度改性PP和PPR的冲击强度

Table 2 Impact strength of modified PP and PPR in different concentrations of NAB-81

聚丙烯	NAB-81/%	冲击强度/(kJ/m²)
PPR(4220), MI=0.3 g/10 min	0	45.5
	0.01	78.3
	0.02	79.1
	0.05	78.6
PPH(1101), MI=0.5 g/10 min	0	15.0
	0.01	44.2
	0.02	47.3
	0.05	46.8

表3 羧酸金属盐NAB-81不同浓度改性PP和PPR的热变形温度

Table 3 HDT of modified PP and PPR in different concentrations of NAB-81

聚丙烯	NAB-81/%	热变形温度/℃
PPR(4220), MI=0.3 g/10 min	0	70.5
	0.01	77.5
	0.02	78.6
	0.05	78.1
PPH(1101), MI=0.5 g/10 min	0	92.7
	0.01	104.5
	0.02	105.6
	0.05	105.1

表4 羧酸金属盐NAB-81不同浓度改性PP和PPR的弯曲性能和拉伸性能

Table 4 Bending and tensile performance of modified PP and PPR in different concentrations of NAB-81

NAB-81/%	PPR(4220), MI=0.3 g/10 min				PPH(1101), MI=0.5 g/10 min
NAB-81/%	弯曲模量/MPa	弹性模量/MPa	拉伸强度/MPa	断裂伸长率/%	弯曲模量/MPa	弹性模量/MPa	拉伸强度/MPa	断裂伸长率/%
0	714.5	728.3	25.3	207.8	1238.7	1371.2	30.2	74.8
0.01	726.8	728.1	25.5	306.4	1265.9	1412.6	33.0	147.6
0.02	726.9	728.6	26.2	330.4	1279.3	1450.4	33.5	118.4
0.05	726.7	728.2	25.6	345.3	1276.5	1438.8	33.5	113.5

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