Structure and Properties of Brominated Butyl Rubber/Nature Rubber(BIIR/NR) Blends Modified with TBIR†

doi:10.7503/cjcu20170676

Abstract

Abstract:

As a new generation of synthetic rubber, trans-1,4-poly(butadiene-co-isoprene) copolymer rubber(TBIR) was used to modify brominated butyl rubber(BIIR)/ nature rubber(NR) blends for high performance inner liner stocks in all steel radial truck tire, and the crosslinking density, filler dispersion, physical and mechanical properties including gas permeability and flexual fatigue resistance of the BIIR/NR/TBIR blends after crosslinking were studied in details. The results indicate that the carbon black filled BIIR/NR/TBIR compounds show increased green strength and modulus with increased TBIR content, and DSC curves prove the crystallizability of TBIR component in the compounds and the crystallization peaks from TBIR can still be detected in the BIIR/NR/TBIR vulcanizates. Blending TBIR with BIIR/NR, the optimum curing time(t₉₀) and the crosslinking density of the compounds slightly reduced. The BIIR/NR/TBIR vulcanizates showed excellent properties, such as improved hot-air aging resistance(10% higher) and air barrier resistance(17% higher), and greatly improved the 1st-class crack resistance(2 to 5 times higher). The mean size of the carbon black aggregates in BIIR/NR vulcanizate after fatigue test became larger than that in BIIR/NR/TBIR vulcanizates. Finally, the structure evaluation of the BIIR/NR/TBIR vulcanizates and its influences in the crack initiation resistance during the dynamic process with periodical stress and strain were discussed in details. TBIR is deemed as an ideal candidate to modify BIIR or BIIR/NR blends for truck tire inner liner stocks with higher crack initiation resistance without deteriorating of other properties.

Key words: Trans-1,4-poly(butadiene-co-isoprene) copolymer rubber, Inner liner, Gas barrier, Flex fatigue property, Aging, Brominated butyl rubber, Nature rubber

TrendMD:

ZHANG Jianping, SONG Liyuan, WANG Hao, WANG Riguo, HE Aihua. Structure and Properties of Brominated Butyl Rubber/Nature Rubber(BIIR/NR) Blends Modified with TBIR^†[J]. Chem. J. Chinese Universities, 2018, 39(6): 1334.

Figures/Tables 13

Fig.1 Stress versus strain curves of BIIR/NR/TBIR compoundsw(BIIR)/w(NR)/w(TBIR): a. 70/30/0; b. 70/20/10; c. 70/10/20; d. 70/0/30.

Fig.2 DSC curves of BIIR/NR/TBIR compounds(A) and vulcanizates(B)w(BIIR)/w(NR)/w(TBIR): a. 100/0/30; b. 100/10/20; c. 100/20/10; d. 100/30/0.

Table 1 Properties of BIIR/NR/TBIR compounds

w(BIIR)/w(NR)/w(TBIR)	Green strength/MPa	Elongation at break(%)	Hardness(Shore A)
70/30/0	0.17	725	30
70/20/10	0.19	519	33
70/10/20	0.33	411	35
70/0/30	0.91	342	40

Table 2 Cure characteristics of BIIR/NR/TBIR compounds

w(BIIR)/w(NR)/w(TBIR)	M_L/(dN·m)	M_H/(dN·m)	M_H-M_L/(dN·m)	t₁₀/min	t₉₀/min	10⁴Crosslink density/ (mol·c $m - 3$ )
70/30/0	1.36	6.84	5.48	6.0	25.3	2.03
70/20/10	1.55	6.32	4.77	6.2	25.0	1.87
70/10/20	1.58	6.29	4.71	5.7	24.5	1.72
70/0/30	1.83	6.59	4.76	4.5	23.4	1.82

Table 2 Cure characteristics of BIIR/NR/TBIR compounds

w(BIIR)/w(NR)/w(TBIR)	M_L/(dN·m)	M_H/(dN·m)	M_H-M_L/(dN·m)	t₁₀/min	t₉₀/min	10⁴Crosslink density/ (mol·c $m - 3$ )
70/30/0	1.36	6.84	5.48	6.0	25.3	2.03
70/20/10	1.55	6.32	4.77	6.2	25.0	1.87
70/10/20	1.58	6.29	4.71	5.7	24.5	1.72
70/0/30	1.83	6.59	4.76	4.5	23.4	1.82

Table 3 Mechanical properties of BIIR/NR/TBIR vulcanizats

w(BIIR)/w(NR)/w(TBIR)	Tensile strength/MPa	Modulus at 100%/MPa	Modulus at 300%/MPa	Tear strength/ (kN·m^-1)	Elongation at break(%)	Rebound(%)
70/30/0	9.0	1.3	3.6	34.5	745	7
70/20/10	8.3	1.2	3.2	33.4	799	7
70/10/20	8.1	1.1	2.9	32.7	835	8
70/0/30	7.1	1.3	3.4	31.1	753	8

Table 4 Properties after hot air ageing(100 ℃, 48 h) of BIIR/NR/TBIR vulcanizats

w(BIIR)/w(NR)/w(TBIR)	Tensile strength/MPa	Modulus at 100%/MPa	Modulus at 300%/MPa	Elongation at break(%)	Ageing coefficient(%)
70/30/0	8.2	1.6	3.9	677	82.8
70/20/10	7.9	1.5	3.6	778	92.7
70/10/20	7.6	1.3	3.3	838	94.2
70/0/30	7.3	1.5	3.8	694	94.8

Fig.3 Nitrogen permeability of BIIR/NR/TBIR vulcanizatesw(BIIR)/w(NR)/w(TBIR): a. 70/30/0; b. 70/20/10; c. 70/10/20; d. 70/0/30.

Fig.4 Flex fatigue resistances of BIIR/NR/TBIR vulcanizates (A) The 1st-class; (B) the 6th-class crack flex times. w(BIIR)/w(NR)/w(TBIR): a. 70/30/0; b. 70/20/10; c. 70/10/20; d. 70/0/30.

Fig.5 DMA curves of BIIR/NR/TBIR vulcanizates(A) G' vs. temperature; (B) G″ vs. temperature; (C) tanδ vs. temperature.

Fig.6 TEM images of BIIR/NR/TBIR blendsw(BIIR)/w(NR)/w(TBIR): (A) 70/30/0; (B) 70/20/10; (C) 70/10/20; (D) 70/0/30.

Table 5 Filler dispersion and mean aggregate size in BIIR/NR/TBIR vulcanizates

w(BIIR)/w(NR)/w(TBIR)	Dispersion(%)	Mean aggregate size/μm
70/30/0	94.3	10.1
70/20/10	96.3	10.2
70/10/20	95.5	10.0
70/0/30	95.1	10.2

Table 6 Filler dispersion and mean aggregate size in BIIR/NR/TBIR vulcanizates after 4×105 times fatigue test

w(BIIR)/w(NR)/w(TBIR)	Dispersion(%)	Mean aggregate size/μm
70/30/0	93.2	11.5
70/20/10	92.8	11.3
70/10/20	94.2	11.0
70/0/30	93.8	10.3

Fig.7 Property radar map of BIIR/NR/TBIR vulcanizates

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