Preparation method of itaconate-butadiene bio-based engineering rubber

Abstract

A preparation method of itaconate-butadiene bio-based engineering rubber belongs to the bio-based engineering rubber area. The bio-based engineering rubber of the present disclosure is formed through chemical crosslinking of copolymers, which are formed by polymerization of itaconate and butadiene emulsion. The number average molecular weight of the itaconate-butadiene copolymer is about 53000-1640000, and weight-average molecular weight is about 110000-2892000. Itaconate-butadiene copolymers are formed by polymerization of itaconate and butadiene emulsion, then and chemical crosslinking of the copolymer is performed to form bio-based engineering rubber using a traditional sulfur vulcanizing system. The bio-based engineering rubber has high molecular weights as well as lower glass-transition temperatures and can be vulcanized using the traditional sulfur vulcanizing system. The bio-based engineering rubber of the present disclosure has same physic-mechanical property as well as processability as compared to rubber prepared using conventional techniques and may be used for manufacturing tire treads and conveyor belts.

Claims

1. A method of preparing bio-based engineering rubber formed by emulsion polymerization of chemically crosslinked itaconate-butadiene copolymers, the method comprising: A: performing the emulsion polymerization of itaconate and butadiene by: mixing itaconate, emulsifier, electrolyte, activator and deionized water in a polymerization reactor, closing the polymerization reactor, removing air from the polymerization reactor using vacuum-pumping, filling the polymerization reactor with nitrogen, repeating mixing, closing, removing and filling operations for 1-5 times, adding butadiene, deoxidant, and initiator to the polymerization reactor and performing reaction for 5-15 hours in the polymerization reactor under 1-20 C., 0.1-5 Mpa, adding a terminator to terminate the reaction and performing demulsification and drying of the terminated reaction via an addition of a demulsifier to obtain a bio-based engineering elastomer raw glue comprising the itaconate-butadiene copolymers, wherein a mass ratio of the itaconate, the butadiene, the emulsifier, the electrolyte, the activator, the deoxidant and the initiator, the terminator and the deionized water is: 100: 1-100:1-10:0.1-5:0.01-5:0.1-5:0.01-5: 1-10:100-1000, a number average molecular weight of the itaconate-butadiene copolymers is about 53000-1640000, a weight-average molecular weight of the itaconate-butadiene copolymers is about 110000-2892000, and a molecular formula of itaconate is: ##STR00002## wherein R.sub.1 and R.sub.2 are H or C.sub.1-10 alkyl, and R.sub.1 R.sub.2 are same or different; and B: performing vulcanization process based on the obtained bio-based engineering elastomer using sulfur as a cross-linking agent in a sulfur vulcanizing system under 140-160 C. to prepare the bio-based engineering rubber comprising the itaconate-butadiene copolymers.

2. The method of claim 1, wherein R1 and R2 are n-butyl, n-amyl or isoamyl.

3. The method of claim 1, wherein the emulsifier comprises at least one of disproportionate sodium abietate, disproportionated potassium rosinate, sodium aliphatate soap, potassium aliphatate soap, sodium dodecyl sulfate, sulfate sodium dodecyl benzene sulfonate, or sodium dodecyl sulfonate.

4. The method of claim 1, wherein the electrolyte comprises at least one of potassium chloride, potassium phosphate, ethylenediaminetetraacetic acid (EDTA), sodium m-dimethylnaphthalenesulfonate (TAOM-L), phosphate, or potassium hydroxide.

5. The method of claim 1, wherein the activator is a mixture of sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid (EDTA) ferric or a mixture of sodium formaldehyde sulfoxylate and ferric sodium ethylenediaminetetraacetate (NaFeEDTA) and initiator mentioned above is p-Menthane Hydroperoxide, tert-butyl hydroperoxide or cumene hydroperoxide.

6. The method of claim 1, wherein the terminator is sodium N, N-dimethyl dithiocarbamate, sodium diethyldithiocarbamate, hydroxylamine or sodium polysulfide.

7. The method of claim 1, wherein the mass ratio of itaconate and butadiene monomer is 100:10 to 100:60.

8. The method of claim 1, wherein the sulfur vulcanizing system comprises vulcanization activator, vulcanization accelerator, and vulcanizator.

9. The method of claim 1, wherein the demulsifier comprises hydrochloric acid.

10. The method of claim 1, wherein the deoxidant comprises sodium hydrosulfite.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a photo itaconate-butadiene bio-based engineering rubber produced by embodiments 4.

(2) FIG. 2 is a .sup.1H-NMR diagram of itaconate-butadiene bio-based engineering rubber produced by embodiments 4, peak at chemical shift 4.94-5.68 ppm indicates that there is double bond exist in itaconate-butadiene bio-based engineering rubber, which provides crosslink points in a later crosslink process.

(3) FIG. 3 is a TEM photo of silica-enhanced itaconate-butadiene bio-based engineering rubber produced by embodiments 11 and shows that filler has good dispersion effect in itaconate-butadiene bio-based engineering rubber.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(4) All materials used in embodiments and comparisons below are sold on the market. Materials used in polymerization process is an analytical reagent, materials in mixing process are chemically pure. Loss factor (tan ) of itaconate-butadiene bio-based engineering rubber in embodiments and rubber compound materials in comparisons is tested through dynamic mechanical analyzer under 80-100 C., 10 Hz, 3 C./min heating rate and 0.1% dynamic stress stretch. The size of test wafer is 20 mm length10 mm width1 mm thickness.

Embodiment 1

(5) Various operations were performed to add 500 g deionized water, 150 g monomethyl itaconate, 3 g soap of potassium aliphatate, 4 g soap of sodium aliphatate, 2 g H.sub.3PO.sub.4, 0.02 g EDTA, 0.25 g TAOM-L, 0.01 g EDTA-Fe and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device, seal the device, vacuumize and fill with nitrogen. Then, 50 g butadiene, 0.02 g sodium dithionite, and 0.03 g hydrogen peroxide p-menthane are added to the device, react 15 hours under 1 C., 0.1 Mpa, add 1 g hydroxylamine to end the reaction to obtain monomethyl itaconate-butadiene bio-based engineering rubber latex. It is poured into 0.1 mol/L hydrochloric acid to finish emulsion breaking and drying process, then dimethyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(6) Further operations include taking 100 g monomethyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 50 g silica and 5 g Si69 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 140 C. to get dimethyl itaconate-butadiene bio-based engineering rubber.

Embodiment 2

(7) Various operations were performed to add 500 g deionized water, 160 g monoethyl itaconate, 5 g soap of potassium aliphatate, 5 g disproportionated rosin sodium soap, 0.3 g K.sub.3PO.sub.4, 0.15 g KCl, 0.03 g EDTA, 0.25 g TAOM-L, 1 g EDTA-Fe.Math.Na and 4 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuumize and fill with nitrogen, continuously operation for 3 times. Then, 40 g butadiene, 0.01 g sodium dithionite, and 0.05 g hydrogen peroxide p-menthane are added to the device, react 10 hours under 5 C., 1 Mpa, add 5 g hydroxylamine to end the reaction to obtain monoethyl itaconate-butadiene bioengineering rubber latex. It is poured into absolute ethyl alcohol to finish emulsion breaking and drying process, then diethyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(8) Further operations include taking 100 g diethyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 40 g silica and 4 g Si69 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get diethyl itaconate-butadiene bio-based engineering rubber.

Embodiment 3

(9) Various operations were performed to add 500 g deionized water, 140 g dibutyl itaconate, 3 g soap of potassium aliphatate, 4 g soap of sodium aliphatate, 0.2 g H.sub.3PO.sub.4, 0.12 g KOH, 0.02 g EDTA, 0.25 g TAOM-L, 0.01 g EDTA-Fe and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuumize and fill with nitrogen, continuously operation for 5 times. Then, 60 g butadiene, 2 g sodium dithionite, and 5 g hydrogen peroxide p-menthane are added to the device, react 8 hours under 5 C., 1 Mpa, add 3 g hydroxylamine to end the reaction to obtain monobutyl itaconate-butadiene bio-based engineering rubber latex. It is poured into 1 wt % calcium chloride solution to finish emulsion breaking and drying process, then dibutyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(10) Further operations include taking 100 g dibutyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g silica and 6 g Si69 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 160 C. to get dibutyl itaconate-butadiene bio-based engineering rubber.

Embodiment 4

(11) Various operations were performed to add 500 g deionized water, 120 g dibutyl itaconate, 3 g soap of potassium aliphatate, 4 g soap of sodium aliphatate, 0.2 g H.sub.3PO.sub.4, 0.12 g KOH, 0.02 g EDTA, 0.25 g TAOM-L, 0.02 g EDTA-Fe and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuumize and fill with nitrogen, continuously operation for 4 time. Then, 80 g butadiene, 0.01 g sodium dithionite, and 0.01 g hydrogen peroxide p-menthane are added to the device, react 9 hours under 5 C., 1 Mpa, add 10 g hydroxylamine to end the reaction to obtain dibutyl itaconate-butadiene bio-based engineering rubber latex. It is poured into 1 wt % calcium chloride solution to finish emulsion breaking and drying process, then dibutyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(12) Further operations include taking 100 g dibutyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g silica and 6 g Si69 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get dibutyl itaconate-butadiene bio-based engineering rubber.

Embodiment 5

(13) Various operations were performed to add 400 g deionized water, 140 g n-amyl itaconate, 5 g disproportionated potassium rosinate, 2 g H.sub.3PO.sub.4, 1.2 g KOH, 0.5 g EDTA, 1.3 g TAOM-L, 0.01 g EDTA-Fe.Math.Na and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuumize and fill with nitrogen, continuously operation for 3 times Then, 60 g butadiene, 0.02 g sodium dithionite, and 0.03 g hydrogen peroxide p-menthane are added to the device, react 10 hours under 5 C., 0.5 Mpa, add 10 g hydroxylamine to end the reaction to obtain di-n-amyl itaconate-butadiene bio-based engineering rubber latex. It is poured into 1 wt % calcium chloride solution to finish emulsion breaking and drying process, then di-n-amyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(14) Further operations include taking 100 g di-n-amyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 80 g silica and 8 g Si69 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get di-n-amyl itaconate-butadiene bio-based engineering rubber.

Embodiment 6

(15) Various operations were performed to add 600 g deionized water, 140 g dibutyl itaconate, 6 g sodium dodecyl sulfate, 0.2 g K.sub.3PO.sub.4, 0.4 g KCl, 0.02 g EDTA, 0.2 g TAOM-L, 0.02 g EDTA-Fe and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuumize and fill with nitrogen, continuously operation for four times. Then, 60 g butadiene, 0.02 g sodium dithionite, and 0.03 g hydrogen peroxide p-menthane are added to the device, react 10 hours under 5 C., 2 Mpa, add 1 g sodium N, N-dimethyl dithiocarbamate to end the reaction to obtain monobutyl itaconate-butadiene bio-based engineering rubber latex. It is poured into 5 wt % calcium chloride solution to finish emulsion breaking and drying process, then dibutyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(16) Further operations include taking 100 g dibutyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g silica and 6 g Si69 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get dibutyl itaconate-butadiene bio-based engineering rubber.

Embodiment 7

(17) Various operations were performed to add 500 g deionized water, 150 g isopentyl itaconate, 3 g soap of potassium aliphatate, 4 g soap of sodium aliphatate, 0.2 g H.sub.3PO.sub.4, 0.12 g KOH, 0.02 g EDTA, 0.25 g TAOM-L, 0.01 g EDTA-Fe and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuumize and fill with nitrogen, continuously operation for 3 times. Then, 50 g butadiene, 0.02 g sodium dithionite, and 0.03 g tert-butyl hydroperoxide are added to the device, react 5 hours under 10 C., 3 Mpa, add 7 g hydroxylamine to end the reaction to obtain diisopentyl itaconate-butadiene bio-based engineering rubber latex. It is poured into ethanol to finish emulsion breaking and drying process, then diisopentyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(18) Further operations include taking 100 g diisopentyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g carbon black N330 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get diisopentyl itaconate-butadiene bio-based engineering rubber.

Embodiment 8

(19) Various operations were performed to add 500 g deionized water, 160 g dibutyl itaconate, 2 g sodium dodecyl benzene sulfonate, 0.2 g K.sub.3PO.sub.4, 0.5 g KCl, 0.02 g EDTA, 0.25 g TAOM-L, 0.01 g EDTA-Fe and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuolize and fill with nitrogen, continuously operation for 2 times. Then, 40 g butadiene, 0.02 g sodium dithionite, and 0.03 g cumene hydroperoxide are added to the device, react 7 hours under 20 C., 5 Mpa, add 1 g hydroxylamine to end the reaction to obtain dibutyl itaconate-butadiene bio-based engineering rubber latex. It is poured into 2 wt % calcium chloride solution to finish emulsion breaking and drying process, then dibutyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(20) Further operations include taking 100 g dibutyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 40 g carbon black N330 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get dibutyl itaconate-butadiene bio-based engineering rubber.

(21) Comparison 1

(22) Further operations include taking 100 g SBR1502 to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g silica and 6 g Si69 homogeneously on two roll mill to get rubber compound, process mold cure under 150 C. to get silica-SBR composite.

(23) Comparison 2

(24) Further operations include taking 100 g nature rubber (Cloudmark 1 #) to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g carbon black N330 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get carbon black-nature rubber composite.

(25) TABLE-US-00001 TABLE 1 testing results of raw rubber performance produced by the embodiments. Data in Table 1 was tested by the national standard test method. number-average weight-average Embodi- Tempera- molecular molecular dispersancy ments ture/ C. weight weight index 1 1 1310452 1862128 1.42 2 5 1422839 2602942 1.83 3 5 1379977 1935832 1.40 4 5 1270000 1860000 1.46 5 5 1128462 2491020 2.11 6 5 927846 2289472 2.07 7 10 840392 1634274 1.94 8 20 573466 1236894 2.16

(26) As is shown in Table 1, itaconate-butadiene bio-based engineering raw rubber produced by the present disclosure has high molecular weight, narrow molecular weight distribution and polymerization is processing at low temperature, it lowers the energy consumption, and it is suitable for industrial manufacture.

(27) TABLE-US-00002 TABLE 2 physical-mechanical properties and dynamic mechanical properties of rubber composite produced by embodiments and comparisons. Data in Table 2 were tested by the national standard test method. 300% stretching Tensilestrength/ Breaking strength/ Shore A permanent tan MPa elongation/% MPa hardness deformation/% 0 C. 60 C. Embodiment 1 13.4 385 10.8 71 20 0.18 0.13 Embodiment 2 18.8 437 13.5 65 16 0.22 0.14 Embodiment 3 21.2 510 11.1 61 16 0.25 0.13 Embodiment 4 28.0 774 9.3 60 16 0.28 0.11 Embodiment 5 25.5 598 10.8 61 14 0.27 0.11 Embodiment 6 23.9 502 9.5 63 16 0.28 0.10 Embodiment 7 20.8 473 8.9 60 16 0.23 0.13 Embodiment 8 17.9 469 9.2 62 18 0.27 0.12 Comparison 1 21.3 438 8.4 78 16 0.17 0.13 Comparison 2 24.7 547 11.7 65 14 0.15 0.12

(28) As is shown in table 2, itaconate-butadiene bio-based engineering rubber produced by the present disclosure has outstanding physical-mechanical properties after reinforcing fillers, tensile strength and breaking elongation performance is reaching or exceeding traditional SBR and natural rubber, it satisfies the higher requirements for tire and conveyor. Moreover, at 0 C., tan of itaconate-butadiene bio-based engineering rubber produced by the present disclosure is much higher than SBR and natural rubber, at 60 C., tan of itaconate-butadiene bio-based engineering rubber produced by the present disclosure is equal to SBR and natural rubber or even lower than them. This indicates that itaconate-butadiene bio-based engineering rubber produced by the present disclosure has outstanding dynamic mechanics performance to make it suitable for producing low rolling resistance and high wet-skid resistance tire rubber material.

Embodiments 9-15

(29) Itaconate-butadiene bio-based engineering rubber produced by embodiments 9-15, inventory of itaconate and butadiene is different, for another reagent, variety, and weight are the same as well as preparation technics. Inventory of itaconate and butadiene are shown in Table 3. Specific steps as follow.

(30) Various operations were performed to add 500 g deionized water, dibutyl itaconate, 3 g soap of potassium aliphatate, 4 g soap of sodium aliphatate, 0.2 g H.sub.3PO.sub.4, 0.12 g KOH, 0.02 g EDTA, 0.25 g TAOM-L, 0.01 g EDTA-Fe and 0.05 g sodium formaldehyde sulfoxylate into a 1 L polymerization device; seal the device, vacuumize and fill with nitrogen, continuously operation for 5 times. Then, butadiene, 0.02 g sodium dithionite, and 0.03 g hydrogen peroxide p-menthane are added to the device, react 8 hours under 5 C., 1 Mpa, add 1 g hydroxylamine to end the reaction to obtain dibutyl itaconate-butadiene bio-based engineering rubber latex. It is poured into 1 wt % calcium chloride solution to finish emulsion breaking and drying process, then dibutyl itaconate-butadiene bio-based engineering raw rubber is obtained.

(31) Further operations include taking 100 g dibutyl itaconate-butadiene bio-based engineering raw rubber mentioned above to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g silica and 6 g Si69 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get dibutyl itaconate-butadiene bio-based engineering rubber.

(32) Comparison 3

(33) Further operations include taking 100 g SBR2503 to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g silica and 6 g Si69 homogeneously on two roll mill to get rubber compound, process mold cure under 150 C. to get silica-SBR composite.

(34) Comparison 4

(35) Further operations include taking 100 g nature rubber (lamination gum) to mix with 5 g zinc oxide, 2 g stearic acid, 1 g sulphur, 0.7 g accelerator M, 1 g accelerator CZ, 60 g carbon black N330 homogeneously on two roll mill to get rubber compound. The mold cure is performed under 150 C. to get carbon black-nature rubber composite.

(36) TABLE-US-00003 TABLE 3 dynamic mechanic property of embodiments and comparisons of the present disclosure. Data in Table 3 were tested by the national standard test method. Inventory of monobutyl Inventory of tan itaconate/g butadiene/g 0 C. 60 C. Embodiment 9 80 20 0.28 0.13 Embodiment 10 70 30 0.28 0.12 Embodiment 11 60 40 0.28 0.11 Embodiment 12 50 50 0.23 0.11 Embodiment 13 40 60 0.20 0.10 Embodiment 14 30 70 0.15 0.09 Embodiment 15 20 80 0.12 0.08 Comparison 3 0.15 0.11 Comparison 4 0.14 0.12

(37) TABLE-US-00004 TABLE 4 physical-mechanical properties of rubber composite produced by embodiments and comparisons. Data in Table 4 were tested by the national standard test method. 300% perma- Tensile Breaking stretching Shore nent de- strength/ elonga- strength/ A hard- forma- MPa tion/% MPa ness tion/% Embodiment 9 15.7 492 7.5 68 40 Embodiment 10 17.4 509 8.8 68 32 Embodiment 11 18.6 590 6.1 60 16 Embodiment 12 21.2 640 6.4 65 16 Embodiment 13 23.6 643 6.5 65 16 Embodiment 14 25.0 774 4.3 71 16 Embodiment 15 24.8 545 9.3 77 10 Comparison 3 17.8 386 9.8 76 16 Comparison 4 20.7 547 10.7 65 14

(38) As is shown in Table 3 and 4, physical-mechanical properties and dynamic mechanical properties of dibutyl itaconate-butadiene bio-based engineering rubber produced by the present disclosure can be adjusted through controlling the inventory of dibutyl itaconate and butadiene. Dibutyl itaconate-butadiene bio-based engineering rubber produced by embodiments satisfies the higher requirements for tire and conveyor. Dibutyl itaconate-butadiene bio-based engineering rubber has the best dynamic mechanical properties when inventory ratio of dibutyl itaconate and butadiene is 60:40 (embodiment 11). At 0 C., tan of this kind of dibutyl itaconate-butadiene bio-based engineering rubber is much higher than SBR and natural rubber; at 60 C., tan of this kind of dibutyl itaconate-butadiene bio-based engineering rubber is equal to SBR and nature rubber. Embodiment 11 is suitable for producing low rolling resistance and high wet-skid resistance tire rubber material.