不同金属盐破乳对丁基橡胶硫化行为的影响

doi:10.11949/0438-1157.20220998

摘要/Abstract

摘要：

为考察金属盐凝固剂对丁基橡胶（isobutylene isoprene rubber，IIR）硫化行为的影响，采用流变仪研究了搅拌破乳及11种金属盐破乳后IIR的硫化历程，并分析了其硫化动力学。研究发现金属盐的阳离子及阴离子种类对硫化过程均有显著影响。与传统Ca²⁺凝固剂相比，过渡金属离子Cu²⁺、Zn²⁺破乳会延长焦烧期及正硫化时间，降低硫化表观活化能，硫化膜储能模量较高。与搅拌破乳相比，主族金属离子Ca²、Mg²⁺、Al³⁺破乳对硫化过程影响较小。阴离子Cl^-及 $N O 3 -$ 有显著的硫化抑制作用，降低硫化表观速率常数，延长正硫化时间；阴离子 $S O 4 2 -$ 和OAc^-对IIR的硫化历程影响较小，相应的IIR硫化胶具有更高的模量。

关键词: 动力学, 流变学, 聚合物加工, 多价金属盐, IIR胶乳, 凝固剂

Abstract:

In order to explore the effect of metal salt demulsifiers on the vulcanization behavior of isobutylene isoprene rubber (IIR), the vulcanization process of IIR demulsified by stirring and 11 metal salts was measured by a rheometer, and the vulcanization kinetics was analyzed. It was found that the cation and anion species of metal salts had significant effects on the vulcanization process. Compared with traditional Ca²⁺ coagulants, the demulsification of transition metal ions Cu²⁺ and Zn²⁺ can prolong the scorch period and positive vulcanization time, reduce the apparent activation energy of vulcanization, and the storage modulus of the vulcanized film is higher. The demulsification by using the main group metal ions Ca²⁺, Mg²⁺, Al³⁺ has little effect on the vulcanization process of IIR. Chloride ion and nitrate ion have significant vulcanization inhibition, reducing the apparent rate constant of vulcanization, and prolonging the positive vulcanization time. Sulfate ion and acetate ion have little effect on the vulcanization process of IIR, and the corresponding IIR vulcanizates have higher modulus.

Key words: kinetics, rheology, polymer processing, multivalent metal salt, IIR emulsion, demulsifier

中图分类号:

TQ 334.2

饶纤纤, 杜淼, 单国荣, 潘鹏举. 不同金属盐破乳对丁基橡胶硫化行为的影响[J]. 化工学报, 2023, 74(2): 756-765.

Xianxian RAO, Miao DU, Guorong SHAN, Pengju PAN. Effect of different metal salt demulsifiers on vulcanization behavior of isobutylene isoprene rubber[J]. CIESC Journal, 2023, 74(2): 756-765.

图/表 8

表1 IIR硫化体系配方

Table 1 Formula of IIR vulcanization system

Types of ingredients	phr of ingredients
IIR latex (solid content)	100.0
S	1.5
ZBEC	1.5
ZMBT	1.5
ZnO	5.0
stearic acid	2.0
4020	1.5

图1 不同金属阳离子破乳IIR的硫化曲线（160℃）

Fig.1 Vulcanization curves of IIR after demulsification by metallic salt with different cations at 160℃

表2 不同金属盐破乳IIR硫化体系的Gmax'、Gmin'、Gmax'-Gmin'、t10、t90、v和凝胶分率（160℃）

Table 2 Gmax'，Gmin'，Gmax'-Gmin'， t10， t90， v and gel fraction of IIR after demulsification with different metallic salt solutions （160℃）

Metallic salts	$G m a x'$ /kPa	$G m i n'$ /kPa	$(G m a x' - G m i n')$ /kPa	t₁₀/min	t₉₀/min	v×10⁵/ (mol/cm³)	Gel fraction/%
stirring	116.09	16.80	99.29	2.0	22.0	2.30±0.60	89.06
MgCl₂	93.32	13.47	79.85	2.5	30.0	4.31±0.50	91.15
CaCl₂	113.96	20.27	93.69	3.0	19.0	2.85±0.80	90.41
CuCl₂	89.09	14.31	74.78	5.5	24.0	1.15±0.70	92.20
ZnCl₂	119.54	13.40	106.14	7.0	38.0	3.75±0.80	90.39
AlCl₃	106.09	14.46	91.63	3.0	21.0	1.55±0.40	90.39
MgSO₄	99.03	18.40	80.63	3.0	14.0	1.52±0.40	90.09
CuSO₄	145.44	24.65	120.79	5.5	27.0	2.56±0.60	89.71
Mg(OAc)₂	91.98	15.22	76.76	2.5	17.0	3.99±1.20	90.96
Cu(OAc)₂	125.45	12.14	113.31	6.0	26.0	2.62±0.50	91.96
Zn(OAc)₂	155.59	18.13	137.46	3.5	30.0	3.27±1.20	88.50
Ca(NO₃)₂	81.96	13.60	68.36	2.0	27.0	4.29±1.0	92.00

表2 不同金属盐破乳IIR硫化体系的Gmax'、Gmin'、Gmax'-Gmin'、t10、t90、v和凝胶分率（160℃）

Table 2 Gmax'，Gmin'，Gmax'-Gmin'， t10， t90， v and gel fraction of IIR after demulsification with different metallic salt solutions （160℃）

Metallic salts	$G m a x'$ /kPa	$G m i n'$ /kPa	$(G m a x' - G m i n')$ /kPa	t₁₀/min	t₉₀/min	v×10⁵/ (mol/cm³)	Gel fraction/%
stirring	116.09	16.80	99.29	2.0	22.0	2.30±0.60	89.06
MgCl₂	93.32	13.47	79.85	2.5	30.0	4.31±0.50	91.15
CaCl₂	113.96	20.27	93.69	3.0	19.0	2.85±0.80	90.41
CuCl₂	89.09	14.31	74.78	5.5	24.0	1.15±0.70	92.20
ZnCl₂	119.54	13.40	106.14	7.0	38.0	3.75±0.80	90.39
AlCl₃	106.09	14.46	91.63	3.0	21.0	1.55±0.40	90.39
MgSO₄	99.03	18.40	80.63	3.0	14.0	1.52±0.40	90.09
CuSO₄	145.44	24.65	120.79	5.5	27.0	2.56±0.60	89.71
Mg(OAc)₂	91.98	15.22	76.76	2.5	17.0	3.99±1.20	90.96
Cu(OAc)₂	125.45	12.14	113.31	6.0	26.0	2.62±0.50	91.96
Zn(OAc)₂	155.59	18.13	137.46	3.5	30.0	3.27±1.20	88.50
Ca(NO₃)₂	81.96	13.60	68.36	2.0	27.0	4.29±1.0	92.00

图2 不同阴离子金属盐破乳后IIR的硫化曲线（160℃）

Fig.2 Vulcanization curves of IIR after demulsification by metallic salt with different anions(160℃)

图3 不同金属阳离子破乳后IIR体系硫化动力学曲线

Fig.3 Vulcanization kinetics curves of IIR after demulsification by metallic salt with different cations

表3 不同金属盐破乳后IIR体系的硫化反应表观速率常数和表观活化能

Table 3 Vulcanization rate constant and vulcanization activation energy of IIR after demulsification with different metallic salt solutions

Metallic salt	K/(10^-3 s^-1)						E_a/(kJ/mol)	R²
Metallic salt	160℃	R²	170℃	R²	180℃	R²	E_a/(kJ/mol)	R²
stirring	1.550±0.034	0.9575	5.820±0.150	0.9831	11.190±0.260	0.9925	161.7±29.4	0.9679
MgCl₂	1.370±0.002	0.9997	3.230±0.008	0.9997	7.410±0.041	0.9994	137.7±0.5	1.0000
CaCl₂	2.270±0.009	0.9988	5.210±0.057	0.9965	10.280±0.065	0.9994	123.4±5.5	0.9980
CuCl₂	1.820±0.006	0.9991	4.000±0.026	0.9983	8.960±0.110	0.9975	130.0±2.6	0.9996
ZnCl₂	1.150±0.004	0.9985	2.300±0.014	0.9974	4.840±0.049	0.9966	95.4±16.2	0.9721
AlCl₃	2.120±0.004	0.9998	4.180±0.011	0.9997	9.210±0.128	0.9967	119.8±6.8	0.9968
MgSO₄	3.250±0.004	0.9991	7.700±0.018	0.9999	15.160±0.320	0.9955	125.7±7.1	0.9968
CuSO₄	1.540±0.006	0.9983	3.290±0.023	0.9976	6.940±0.085	0.9969	122.8±1.0	0.9999
Mg(OAc)₂	2.320±0.026	0.9914	4.790±0.055	0.9962	10.140±0.092	0.9989	120.3±2.7	0.9995
Cu(OAc)₂	1.710±0.004	0.9995	3.550±0.011	0.9996	6.920±0.041	0.9993	114.1±1.5	0.9998
Zn(OAc)₂	1.310±0.004	0.9990	2.600±0.010	0.9991	5.320±0.037	0.9986	114.3±2.9	0.9994
Ca(NO₃)₂	1.320±0.020	0.9757	4.090±0.092	0.9813	11.830±0.084	0.9994	179.0±0.9	1.0000

图4 不同金属阳离子破乳后IIR硫化的lnK-1/T曲线

Fig.4 lnK-1/T curves of IIR after demulsification by metallic salt with different cations

图5 不同阴离子金属盐破乳后IIR体系的lnK-1/T曲线

Fig.5 lnK-1/T curves of IIR after demulsification by metallic salt with different anions

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