Method for preparing syndiotactic poly1,2-butadiene thermoplastic elastomer

Abstract

The invention relates to a method for preparing a syndiotactic poly1,2-butadiene thermoplastic elastomer, which comprises the following steps: initiating the polymerization of 1,3-butadiene monomer in hexane solution of a synthetic rubber through the addition of 1,2-configurational units by using iron catalysts to form a uniform blend of 1,2-butadiene and synthetic rubber, wherein the catalysts comprise iron isooctanoate or iron naphthenate, diethyl phosphate, triisobutyl aluminium and aluminium triethyl; the adding sequence of the catalysts is that any components are combined or two aluminumalkyls are mixed first and then combined with the other two components optionally; in a polymerization system, every 1,000 millilitres of hexane solution contains 90 to 140 grams of 1,3-butadiene monomer, and the adding amount of the rubber is 0.1 to 25 grams; and the polymerization initiating temperature is 60 to 90 DEG C. The blend has the properties of the typical thermoplastic elastomers and can be used for modifying thin films, shoe soles, tubular materials, rubbers and plastics.

Description

technical field

[0001] The invention relates to a preparation method of syndiotactic poly-1,2-butadiene thermoplastic elastomer. Background technique

[0002] The 1,3-butadiene monomer undergoes addition polymerization with 1,2-configuration units under the action of different catalysts, and high polymers with the following configurations can be obtained.

[0003] Isotactic:

[0004]

[0005] Syndiotactic:

[0006]

[0007] Atactic:

[0008]

[0009] Among them, random poly-1,2-butadiene is rubbery at room temperature, and was industrialized in the 1980s using lithium-based catalysts. Isotactic 1,2-polybutadiene has so far not been satisfactorily synthesized. Syndiotactic poly-1,2-butadiene is mainly prepared by a catalyst composed of Ti, Mo, Co, Cr, Fe and other metal element compounds and aluminum compounds.

[0010] In the 1970s, people carried out in-depth research on the synthesis catalyst and application of syndiotactic (or syndiotactic) poly-1,2-butadien...

Examples

Embodiment 1～6

[0033]The synthetic rubber added in embodiment 1 and 6 is Buna-CB24 neodymium system butadiene rubber, and the added amount is 0.3g, 75g; the added synthetic rubber in embodiment 2, 3 is high vinyl polybutadiene rubber, and the added amount is 5g . Other conditions are as follows: Add dry synthetic rubber into a 5L stainless steel kettle, replace the reactor with nitrogen with a purity of 99.99% for 5 times, then add 2500ml of dry hexane solvent oil, start stirring and heat up to 90°C, wait for the added After the micelle is completely converted into a uniform glue solution (about 24 hours), the temperature of the reactor is lowered to room temperature, and 455ml (300g) of 1,3-butadiene monomer is added thereto, and the temperature is raised to 70° C. of polymerization initiation temperature, and then Add 0.56mmol of iron isooctanoate, (3.00mmol of triisobutylaluminum+7.00mmol of triethylaluminum) and 1.67mmol of diethyl phosphite in sequence, and at the same time, use N 2 Ma...

Embodiment 7～12

[0038] In Examples 7 to 9, the order of catalyst addition is iron isooctanoate, diethyl phosphite, (triisobutylaluminum+triethylaluminum); triisobutylaluminum, iron isooctanoate, triethylaluminum, Diethyl phosphite; Triethylaluminum, iron isooctanoate, triisobutylaluminum, diethyl phosphite, other conditions are the same as in Example 4, and the main properties are shown in Table 3.

[0039] In Examples 10 to 12, the amount of catalyst added is 0.56 mmol of iron naphthenate, (2.00 mmol of triisobutylaluminum+8.00 mmol of triethylaluminum), 1.67 mmol of diethyl phosphite; 0.56 mmol of iron isooctanoate, ( Triisobutylaluminum 3.00mmol+triethylaluminum 7.00mmol), diethyl phosphite 2.24mmol; iron isooctanoate 0.56mmol, (triisobutylaluminum 5.00mmol+triethylaluminum 5.00mmol), diethyl phosphite 1.67mmol, other conditions are with embodiment 4, and main performance is shown in Table 3.

[0040] table 3

[0041]

[0042]

Embodiment 13

[0044] The amount of catalyst added is 0.84mmol of iron isooctanoate, 2.50mmol of diethyl phosphite, (7.50mmol of triisobutylaluminum+17.50mmol of triethylaluminum), and other conditions are the same as in Example 6. The obtained polymer was rubber with a yield of 85% and no crystalline melting peak.

technical field

[0001] The invention relates to a preparation method of syndiotactic poly-1,2-butadiene thermoplastic elastomer. Background technique

[0002] The 1,3-butadiene monomer undergoes addition polymerization with 1,2-configuration units under the action of different catalysts, and high polymers with the following configurations can be obtained.

[0003] Isotactic:

[0004]

[0005] Syndiotactic:

[0006]

[0007] Atactic:

[0008]

[0009] Among them, random poly-1,2-butadiene is rubbery at room temperature, and was industrialized in the 1980s using lithium-based catalysts. Isotactic 1,2-polybutadiene has so far not been satisfactorily synthesized. Syndiotactic poly-1,2-butadiene is mainly prepared by a catalyst composed of Ti, Mo, Co, Cr, Fe and other metal element compounds and aluminum compounds.

[0010] In the 1970s, people carried out in-depth research on the synthesis catalyst and application of syndiotactic (or syndiotactic) poly-1,2-butadien...

Examples

Embodiment 1～6

[0033]The synthetic rubber added in embodiment 1 and 6 is Buna-CB24 neodymium system butadiene rubber, and the added amount is 0.3g, 75g; the added synthetic rubber in embodiment 2, 3 is high vinyl polybutadiene rubber, and the added amount is 5g . Other conditions are as follows: Add dry synthetic rubber into a 5L stainless steel kettle, replace the reactor with nitrogen with a purity of 99.99% for 5 times, then add 2500ml of dry hexane solvent oil, start stirring and heat up to 90°C, wait for the added After the micelle is completely converted into a uniform glue solution (about 24 hours), the temperature of the reactor is lowered to room temperature, and 455ml (300g) of 1,3-butadiene monomer is added thereto, and the temperature is raised to 70° C. of polymerization initiation temperature, and then Add 0.56mmol of iron isooctanoate, (3.00mmol of triisobutylaluminum+7.00mmol of triethylaluminum) and 1.67mmol of diethyl phosphite in sequence, and at the same time, use N 2 Ma...

Embodiment 7～12

[0038] In Examples 7 to 9, the order of catalyst addition is iron isooctanoate, diethyl phosphite, (triisobutylaluminum+triethylaluminum); triisobutylaluminum, iron isooctanoate, triethylaluminum, Diethyl phosphite; Triethylaluminum, iron isooctanoate, triisobutylaluminum, diethyl phosphite, other conditions are the same as in Example 4, and the main properties are shown in Table 3.

[0039] In Examples 10 to 12, the amount of catalyst added is 0.56 mmol of iron naphthenate, (2.00 mmol of triisobutylaluminum+8.00 mmol of triethylaluminum), 1.67 mmol of diethyl phosphite; 0.56 mmol of iron isooctanoate, ( Triisobutylaluminum 3.00mmol+triethylaluminum 7.00mmol), diethyl phosphite 2.24mmol; iron isooctanoate 0.56mmol, (triisobutylaluminum 5.00mmol+triethylaluminum 5.00mmol), diethyl phosphite 1.67mmol, other conditions are with embodiment 4, and main performance is shown in Table 3.

[0040] table 3

[0041]

[0042]

Embodiment 13

[0044] The amount of catalyst added is 0.84mmol of iron isooctanoate, 2.50mmol of diethyl phosphite, (7.50mmol of triisobutylaluminum+17.50mmol of triethylaluminum), and other conditions are the same as in Example 6. The obtained polymer was rubber with a yield of 85% and no crystalline melting peak.

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