CATALYTIC SYSTEM AND USE THEREOF, AND PREPARATION METHOD OF SYNDIOTACTIC 1,2-POLYBUTADIENE (s-PB)

Abstract

The present disclosure relates to the technical field of preparation of syndiotactic 1,2-polybutadiene (s-PB), in particular to a catalytic system and use thereof, and a preparation method of s-PB. In the present disclosure, the catalytic system includes an iron-containing organic compound, an azodicyano compound, an organoaluminum compound, and a free radical scavenger; where an iron element in the iron-containing organic compound, the azodicyano compound, the organoaluminum compound, and the free radical scavenger have a molar ratio of 1:(0.5-10):(5-100):(1-1000); and the free radical scavenger is selected from the group consisting of a sterically hindered phenol, a sterically hindered amine, and a phosphorus-containing antioxidant. The catalytic system can prepare the s-PB with a high activity at a high temperature, and the s-PB has a melting point of 60° C. to 130° C. with an extremely low gel content or even no gelation.

Claims

1. A catalytic system comprising: an iron-containing organic compound, an azodicyano compound, an organoaluminum compound, and a free radical scavenger; wherein: an iron element in the iron-containing organic compound, the azodicyano compound, the organoaluminum compound, and the free radical scavenger have a molar ratio of 1:(0.5-10):(5-100):(1-1000); and the free radical scavenger is selected from the group consisting of a sterically hindered phenol, a sterically hindered amine, and a phosphorus-containing antioxidant.

2. The catalytic system according to claim 1, wherein the iron-containing organic compound comprises an iron-containing carboxylate and/or an iron-containing complex.

3. The catalytic system according to claim 2, wherein the iron-containing carboxylate is one or more selected from the group consisting of iron naphthenate, iron neodecanoate, and iron(III) 2-ethylhexanoate; and the iron-containing complex is iron acetylacetonate.

4. The catalytic system according to claim 1, wherein the azodicyano compound is one or more selected from the group consisting of azobisisobutyronitrile (AIBN), 2,2′-azobis(2-methylbutyronitrile) (AMBN), 2,2′-azobis-(2,4-dimethylvaleronitrile) (ABVN), and 1,1′-azobis(cyclohexanecarbonitrile) (ACCN).

5. The catalytic system according to claim 1, wherein the organoaluminum compound is one or more selected from the group consisting of triethylaluminum (TEA), triisobutylaluminum (TIBA), diisobutylaluminum hydride (DIBAH), and diisobutylaluminum chloride (DIBAC).

6. The catalytic system according to claim 1, wherein the free radical scavenger is one or more selected from the group consisting of an antioxidant 2264, an antioxidant 264, an antioxidant 1010, an antioxidant 1076, an antioxidant THP24, an antioxidant 3010, an antioxidant 168, an antioxidant RD, an antioxidant 1024, an antioxidant 4010, an antioxidant 4020, and an antioxidant H.

7. (canceled)

8. A preparation method of s-PB, the method comprising the following steps: mixing a catalytic system with butadiene to conduct polymerization to obtain the s-PB; wherein: the butadiene is in a form selected from the group consisting of a liquid butadiene bulk and a butadiene solution; the butadiene solution has a hydrocarbon organic solvent; and the catalytic system comprises: an iron-containing organic compound, an azodicyano compound, an organoaluminum compound, and a free radical scavenger; wherein: an iron element in the iron-containing organic compound, the azodicyano compound, the organoaluminum compound, and the free radical scavenger have a molar ratio of 1:(0.5-10):(5-100):(1-1000); and the free radical scavenger is selected from the group consisting of a sterically hindered phenol, a sterically hindered amine, and a phosphorus-containing antioxidant.

9. The preparation method according to claim 8, wherein the catalytic system has the iron element and the butadiene at a molar ratio of 1:(1000-100000).

10. The preparation method according to claim 8, wherein the iron-containing organic compound comprises an iron-containing carboxylate and/or an iron-containing complex.

11. The preparation method according to claim 10, wherein the iron-containing carboxylate is one or more selected from the group consisting of iron naphthenate, iron neodecanoate, and iron(III) 2-ethylhexanoate; and the iron-containing complex is iron acetylacetonate.

12. The preparation method according to claim 8, wherein the azodicyano compound is one or more selected from the group consisting of azobisisobutyronitrile (AIBN), 2,2′-azobis(2-methylbutyronitrile) (AMBN), 2,2′-azobis-(2,4-dimethylvaleronitrile) (ABVN), and 1,1′-azobis(cyclohexanecarbonitrile) (ACCN).

13. The preparation method according to claim 8, wherein the organoaluminum compound is one or more selected from the group consisting of triethylaluminum (TEA), triisobutylaluminum (TIBA), diisobutylaluminum hydride (DIBAH), and diisobutylaluminum chloride (DIBAC).

14. The preparation method according to claim 8, wherein the free radical scavenger is one or more selected from the group consisting of an antioxidant 2264, an antioxidant 264, an antioxidant 1010, an antioxidant 1076, an antioxidant THP24, an antioxidant 3010, an antioxidant 168, an antioxidant RD, an antioxidant 1024, an antioxidant 4010, an antioxidant 4020, and an antioxidant H.

15. The preparation method according to claim 10, wherein the catalytic system has the iron element and the butadiene at a molar ratio of 1:(1000-100000).

16. The preparation method according to claim 11, wherein the catalytic system has the iron element and the butadiene at a molar ratio of 1:(1000-100000).

17. The preparation method according to claim 12, wherein the catalytic system has the iron element and the butadiene at a molar ratio of 1:(1000-100000).

18. The preparation method according to claim 13, wherein the catalytic system has the iron element and the butadiene at a molar ratio of 1:(1000-100000).

19. The preparation method according to claim 14, wherein the catalytic system has the iron element and the butadiene at a molar ratio of 1:(1000-100000).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] FIG. 1 shows a .sup.1H NMR spectrum of s-PB in Example 25;

[0026] FIG. 2 shows a .sup.1H NMR spectrum of s-PB in Example 3;

[0027] FIG. 3 shows a .sup.1H NMR spectrum of s-PB in Example 15;

[0028] FIG. 4 shows a DSC chart of s-PB in Example 3;

[0029] FIG. 5 shows a DSC chart of s-PB in Example 25; and

[0030] FIG. 6 shows a DSC chart of s-PB in Example 8.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] The present disclosure provides a catalytic system, including an iron-containing organic compound (denoted as A), an azodicyano compound (denoted as B), an organoaluminum compound (denoted as C), and a free radical scavenger (denoted as D); where

[0032] an iron element in the iron-containing organic compound, the azodicyano compound, the organoaluminum compound, and the free radical scavenger have a molar ratio of 1:(0.5-10):(5-100):(1-1000); and

[0033] the free radical scavenger is selected from the group consisting of a sterically hindered phenol, a sterically hindered amine, and a phosphorus-containing antioxidant.

[0034] In the present disclosure, all components are commercially available products well known to those skilled in the art unless otherwise specified.

[0035] In the present disclosure, the iron-containing organic compound includes preferably an iron-containing carboxylate and/or an iron-containing complex, and the iron-containing carboxylate has preferably divalent iron or trivalent iron; the iron-containing carboxylate is preferably one or more selected from the group consisting of iron naphthenate, iron neodecanoate, and iron(III) 2-ethylhexanoate; the iron-containing complex is preferably iron acetylacetonate; and when the iron-containing organic compound is two or more of the above-mentioned specific selections, there is no special limitation on a proportion of the above-mentioned specific substances, and any proportion can be used.

[0036] In the present disclosure, the azodicyano compound is preferably one or more selected from the group consisting of AIBN, AMBN, ABVN, and ACCN; and when the azodicyano compound is two or more of the above-mentioned specific selections, there is no special limitation on a proportion of the above-mentioned specific substances, and any proportion can be used.

[0037] In the present disclosure, the organoaluminum compound is preferably one or more selected from the group consisting of TEA, TIBA, DIBAH, and DIBAC; and when the organoaluminum compound is two or more of the above-mentioned specific selections, there is no special limitation on a proportion of the above-mentioned specific substances, and any proportion can be used.

[0038] In the present disclosure, the free radical scavenger is preferably one or more selected from the group consisting of an antioxidant 2264, an antioxidant 264, an antioxidant 1010, an antioxidant 1076, an antioxidant THP24, an antioxidant 3010, an antioxidant 168, an antioxidant RD, an antioxidant 1024, an antioxidant 4010, an antioxidant 4020, and an antioxidant H; and when the free radical scavenger is two or more of the above-mentioned specific selections, there is no special limitation on a proportion of the above-mentioned specific substances, and any proportion can be used.

[0039] In the present disclosure, an iron element in the iron-containing organic compound, the azodicyano compound, the organoaluminum compound, and the free radical scavenger have a molar ratio of preferably 1:(0.5-10):(5-100):(1-1000), more preferably 1:(1-4):(10-50):(10-100), and most preferably 1:(2-3):(30-40):(30-60).

[0040] In the present disclosure, each component in the catalytic system is preferably packaged independently before use; and when applied, the components are mixed preferably in sequence.

[0041] The present disclosure further provides use of the catalytic system in preparation of s-PB.

[0042] The present disclosure further provides a preparation method of s-PB, including the following steps:

[0043] mixing a catalytic system with butadiene to conduct polymerization to obtain the s-PB; where

[0044] the butadiene is in a form selected from the group consisting of a liquid butadiene bulk and a butadiene solution;

[0045] the butadiene solution has a hydrocarbon organic solvent; and

[0046] the catalytic system is the catalytic system described in the above technical solution.

[0047] In the present disclosure, the butadiene is in a form selected from the group consisting of a liquid butadiene bulk and a butadiene solution; the butadiene solution has preferably a hydrocarbon organic solvent, more preferably an aliphatic hydrocarbon organic solvent or an aromatic hydrocarbon organic solvent; the aliphatic hydrocarbon organic solvent is preferably one or more selected from the group consisting of hexane, cyclohexane, pentane, heptane, and octane, more preferably the hexane and the cyclohexane; the aromatic hydrocarbon organic solvent is preferably one or more selected from the group consisting of benzene, toluene, and xylene; and when the hydrocarbon organic solvent is two or more of the above-mentioned specific selections, there is no special limitation on a proportion of the above-mentioned specific substances, and any proportion can be used.

[0048] In the present disclosure, the butadiene solution has the butadiene and the hydrocarbon organic solvent at a dosage ratio of preferably 1 g:8.4 mL.

[0049] In the present disclosure, the mixing is conducted preferably in a nitrogen atmosphere.

[0050] In the present disclosure, the catalytic system has the iron element and the butadiene at a molar ratio of preferably 1:(1000-100000), more preferably 1:(5000-50000), and most preferably 1:(10000-30000).

[0051] In the present disclosure, the mixing is conducted preferably by: adding each component in the catalytic system to the butadiene in any sequence, more preferably by: adding the A, the B, the C, and the D to the butadiene in an order of A, C, B, and D or in an order of A, C, D, and B; alternatively, two or more components in the catalytic system are mixed and aged, and then added to the butadiene.

[0052] In the present disclosure, the polymerization is conducted at preferably 30° C. to 150° C., more preferably 50° C. to 100° C. for preferably 0.1 h to 10 h, more preferably 0.5 h to 3 h.

[0053] In the present disclosure, after the polymerization is completed, the reaction is preferably terminated by an ethanol solution of HCl with a mass concentration of 1%.

[0054] In the present disclosure, after the reaction is terminated, filtration and vacuum drying are preferably conducted in sequence.

[0055] In the present disclosure, s-PB prepared by the preparation method is preferably used in manufacture of shoe soles, tire treads, sponges, or foamed tire treads.

[0056] The catalytic system and the use thereof, and the preparation method of s-PB provided by the present disclosure will be described in detail below with reference to examples, but these examples should not be construed as limiting the scope of the present disclosure.

[0057] Note: in the examples and comparative examples, a gel content is tested according to a standard of SH/T 1050-2014. In the tables, “-” means no test; [BD]/[Fe] represents the molar ratio of butadiene and iron; [Al]/[Fe] represents the molar ratio of Al and Fe; [OH]/[Al] represents the molar ratio of OH groups and Al in the free radical scavenger; and [P]/[Al] represents the molar ratio of P and Al in the antioxidant 3010.

Examples 1 to 6

[0058] Under a nitrogen atmosphere, a butadiene solution containing 84 mL of dry hexane and 10 g of dry butadiene was added to a single-neck reaction flask subjected to bake-drying; iron acetylacetonate, TIBA, AIBN, and an antioxidant 3010 were added in sequence (a dosage of each component was shown in Table 1), and a resulting mixture was subjected to polymerization in a constant-temperature water bath at 50° C. for 2 h; the reaction was terminated by an ethanol solution of HCl with a mass concentration of 1% and filtration was conducted; an obtained solid product was vacuum-dried at 60° C. to a constant weight, so as to obtain s-PB (relevant physicochemical parameters of the s-PB were shown in Table 1).

TABLE-US-00001 TABLE 1 Raw material dosage and physicochemical parameters of s-PB 1,2- Iron Antioxidant Melting structure Gel acetylacetonate AIBN TIBA 3010 Yield point content Crystallinity content Ex. (mmol) (mmol) (mmol) (mmol) [Al]/[Fe] [P]/[Al] (%) (° C.) (%) (%) (%) 1 0.0185 0.0093 0.093 0.047 5 1 3.6 — — — — 2 0.0185 0.0185 0.37 0.185 20 1 76.3 130.6 58.6 6.3 0 3 0.0185 0.037 0.74 0.37 40 1 95.0 129.7 81.0 20.6 0 4 0.0185 0.093 0.37 0.185 20 1 99.0 72.3 64.5 2.3 0 5 0.0185 0.148 0.555 0.278 30 1 36.9 — — — — 6 0.0185 0.185 0.37 0.185 20 1 16.3 — — — — Note: [BD]/[Fe] = 10000;

[0059] FIG. 2 showed a .sup.1NMR spectrum of the s-PB in Example 3. It was seen from FIG. 2 that the s-PB had a 1,2-structure content of 81%; and

[0060] FIG. 4 showed a DSC chart of the s-PB in Example 3. It was seen from FIG. 4 that the s-PB had a melting point of 129.7° C.

Example 7

[0061] This example referred to Examples 1 to 6, and the difference was only that: after obtaining the butadiene solution, 0.185 mmol of iron(III) 2-ethylhexanoate, 3.7 mmol of TIBA, 0.185 mmol of an antioxidant 1076, and 0.37 mmol of AIBN were successively added to obtain 9.514 g of s-PB (with a yield of 95.14%, a melting point of 77.6° C., a 1,2-structure content of 64.6%, a crystallinity of 2.2%, and a gel content of 1.2%).

Examples 8 to 13

[0062] These examples referred to Example 7, the difference was that: compositions of the catalytic systems were different, and compositions of the catalytic systems in Examples 8 to 13 were shown in Table 2, and physicochemical parameters of the prepared s-PB were shown in Table 2:

TABLE-US-00002 TABLE 2 Raw material dosage and physicochemical parameters of s-PB 1,2- Iron Free radical Melting structure Gel acetylacetonate AIBN TIBA scavenger Yield point content Crystallinity content Ex. (mmol) (mmol) (mmol) (mmol) [BD]/[Fe] (%) (° C.) (%) (%) (%) 8 0.093 0.185 1.85 Antioxidant 0.2 95.2 71.8 75.4 2.3 1.12 264 (0.093) 9 0.037 0.074 0.74 Antioxidant 0.5 93.1 85.6 74.6 5.7 2.2 1076 (0.037) 10 0.0185 0.037 0.37 Antioxidant 1 87.3 88.4 69.4 5.2 0 2264 (0.0185) 11 0.0093 0.0185 0.185 Antioxidant 2 73.3 113.1 64.3 4.6 0 THP24 (0.0093) 12 0.0074 0.0074 0.144 Antioxidant 5 46.7 — — — — 168 (0.0074) 13 0.0037 0.0037 0.074 Antioxidant 10 17.1 — — — — 1024 (0.0037) Note: [Al]/[Fe] = 20:1;

[0063] FIG. 6 showed a DSC chart of the s-PB in Example 8. As was seen from FIG. 6, the s-PB had a melting point of 71.8° C.

Examples 14 to 18

[0064] These examples referred to Examples 1 to 6, and the difference was that: after obtaining the butadiene solution, iron naphthenate, TIBA, an antioxidant 1010 ([OH]/[Al]=1:1), and AIBN were added in sequence to obtain s-PB; physicochemical parameters of the s-PB were shown in Table 3:

TABLE-US-00003 TABLE 3 Raw material dosage and physicochemical parameters of s-PB 1,2- Iron Melting structure Gel acetylacetonate AIBN TIBA [OH] Yield point content Crystallinity content Ex. (mmol) (mmol) (mmol) (mmol) [AL]/[Fe] (%) (° C.) (%) (%) (%) 14 0.0185 0.037 0.185 0.185 10 31.0 — — — — 15 0.0185 0.037 0.37 0.37 20 82.5 91.4 57.7 3.0 1.3 16 0.0185 0.037 0.555 0.555 30 82.7 93.6 64.3 5.1 2.0 17 0.0185 0.037 1.11 1.11 60 89.2 103.2 71.4 5.7 2.2 18 0.0185 0.037 1.85 1.85 100 93.2 104.1 71.6 7.8 3.6 Note: [BD]/[Fe] = 10000; antioxidant 1010 ([OH]/[Al] = 1:1);

[0065] FIG. 3 showed a .sup.1H NMR chart of the s-PB in Example 15. As was seen from FIG. 3, the s-PB had a microscopic 1,2-structure content of 57.7%.

Example 19

[0066] This example referred to Examples 1 to 6, and the difference was that: after obtaining the butadiene solution, 0.185 mmol of iron neodecanoate, 0.37 mmol of TEA, 18.5 mmol of an antioxidant 1076, and 0.37 mmol of ABVN were sequentially added to obtain 5.7 g of s-PB (with a yield of 57%, a melting point of 97.6° C., a 1,2-structure content of 65.4%, a crystallinity of 2.7%, and a gel content of 0).

Example 20

[0067] This example referred to Examples 1 to 6, and the difference was that: after obtaining the butadiene solution, 0.0185 mmol of iron(III) 2-ethylhexanoate, 0.37 mmol of DIBAH, 0.0185 mmol of an antioxidant 1076, and 0.037 mmol of ACCN were sequentially added to obtain 8.7 g of s-PB (with a yield of 87%, a melting point of 94.3° C., a 1,2-structure content of 55.4%, a crystallinity of 2.1%, and a gel content of 0).

Examples 21 to 24

[0068] Under a nitrogen atmosphere, a toluene solution of 2 g/20 mL butadiene was added to a single-neck reaction flask subjected to bake-drying; 0.0037 mmol of iron(III) 2-ethylhexanoate, 0.074 mmol of TIBA, 0.0074 mmol of AIBN, and 0.0037 mmol of a free radical scavenger (types of the free radical scavenger were shown in Table 4) were added in sequence, and a resulting mixture was subjected to polymerization in a constant-temperature water bath at 90° C. for 4 h; the reaction was terminated by an ethanol solution of HCl with a mass concentration of 1% and filtration was conducted; an obtained solid product was vacuum-dried at 60° C. to a constant weight, so as to obtain s-PB (relevant physicochemical parameters of the s-PB were shown in Table 4).

TABLE-US-00004 TABLE 4 Types of sterically hindered amines and physicochemical parameters of s-PB Melting 1,2-structure Gel Types of free radical Yield point content Crystallinity content Ex. scavenger [Al]/[Fe] [NH]/[Fe] (%) (° C.) (%) (%) (%) 21 Antioxidant RD 20 1 93.6 110.6 67.5 2.3 0 22 Antioxidant 4020 20 2 50.7 121.3 55.6 3.2 0 23 Antioxidant 4010 20 2 77.5 123.4 62.3 3.7 0 24 Antioxidant H 20 2 33.6 127.1 68.4 4.4 0 Note: [BD]/[Fe] = 10000;

Example 25

[0069] This example referred to Examples 1 to 6, and the difference was that: after obtaining the butadiene solution, 0.0185 mmol of iron(III) 2-ethylhexanoate, 0.37 mmol of DIBAC, and 0.037 mmol of AIBN were added sequentially; a mixture was heated in a constant-temperature water bath at 70° C. for 10 min, added with 0.0185 mmol of an antioxidant 168, and subjected to polymerization in a constant-temperature water bath at 70° C. for 4 h to obtain 6.4 g of s-PB (with a yield of 64.0%, a melting point of 46.1° C. and 59.8° C. (FIG. 5), a 1,2-structure content of 78.7% (FIG. 1), and a gel content of 0.5%).

Comparative Example 1

[0070] Under a nitrogen atmosphere, a butadiene solution containing 84 mL of dry hexane and 10 g of dry butadiene was added to a single-neck reaction flask subjected to bake-drying; 0.0185 mmol of iron(III) 2-ethylhexanoate, 0.37 mmol of TIBA, and 0.037 mmol of AIBN were added in sequence, and a resulting mixture was subjected to polymerization in a constant-temperature water bath at 50° C. for 2 h; the reaction was terminated by an ethanol solution of HCl with a mass concentration of 1%, and filtration and drying were conducted; an obtained solid product was vacuum-dried at 60° C. to a constant weight, so as to obtain 9.95 g of s-PB (with a yield of 99.50% and a gel content of 78.2%).

Comparative Examples 2 to 4

[0071] These examples referred to Comparative Example 1, the difference was that: different types of azodicyano compounds were used, as shown in Table 5:

TABLE-US-00005 TABLE 5 Types of azodicyano compounds and physicochemical parameters of s-PB in Comparative Examples 2 to 4 1,2- Types of Melting structure Gel azodicyano Yield point content Crystallinity content Ex. compounds [Al]/[Fe] [CN]/[Fe] (%) (° C.) (%) (%) (%) Comp. Ex. 2 AMBN 20 2 93.6 123.6 67.5 2.3 65.2 Comp. Ex. 3 ABVN 20 2 90.7 121.3 58.6 3.2 57.2 Comp. Ex. 4 ACCN 20 2 87.5 123.4 62.3 3.7 52.1

[0072] The above descriptions are merely preferred implementations of the present disclosure. It should be noted that a person of ordinary skill in the art may further make several improvements and modifications without departing from the principle of the present disclosure, but such improvements and modifications should be deemed as falling within the protection scope of the present disclosure.