Process for the preparation of branched polybutadiene with a high content of 1,4-cis units

A technology for polybutadiene and butadiene, which is applied in the field of preparation of branched polybutadiene with high 1,4-cis unit content, can solve the difficulty of feeding, the preparation of catalyst is complicated, and has no practicability And other issues

Active Publication Date: 2011-04-27
POLIMERI EUROPA SPA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the preparation of the above-mentioned catalysts is complicated and not practical, mainly due to the use of large amounts of aluminoxane; moreover, butadiene must be added to the pre-prepared catalyst to prepare the pre-polymerized catalyst, resulting in The association of the polar end groups of the β forms a very viscous solution, so it is very difficult to feed the above prefabricated catalyst from the preparation vessel into the polymerization reactor in industrial practice

Method used

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  • Process for the preparation of branched polybutadiene with a high content of 1,4-cis units
  • Process for the preparation of branched polybutadiene with a high content of 1,4-cis units
  • Process for the preparation of branched polybutadiene with a high content of 1,4-cis units

Examples

Experimental program
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Effect test

Embodiment

[0049] Polymer Characterization

[0050] Mooney viscosity, according to ASTM D 1646 method;

[0051] Analysis of microstructure (cis content) by I.R. spectroscopy according to internal method;

[0052] · Absolute viscosity, measured in 5% w / w styrene solution at T=25°C;

[0053] Determination of molecular weight distribution (MWD) by GPC in tetrahydrofuran at T=25°C according to in-house method;

[0054] The determination of the average molecular weight and the measurement of the degree of branching is by means of the GPC / MALLS technique. By coupling a multi-angle light scattering detector (MALLS) to a conventional SEC / RI elution system, absolute measurements of the molecular weight and radius of gyration of macromolecules separated by a chromatographic system can be performed simultaneously; The amount of light scattering can be used directly to obtain its molecular weight, and the angular change of said scattering is directly related to its average size. The basic rela...

Embodiment 7-11

[0097] Examples 7-11 (polymers F, G, H, I, L synthesized in continuous reactors)

[0098] It has been shown that the use of different types of neodymium tertiary carboxylates leads to a gradual improvement in the rate of polymerization in a manner inversely proportional to the content of proton-donating species. Specifically and similarly to that observed in batch reactors, the decrease in water content leads to a gradual decrease in the Mw / Mn index.

[0099] However, unlike the batch tests performed above, for a particularly clean catalyst, at the same Mooney value, a gradual decrease in the viscosity in styrene due to the degree of branching can be observed, via g M A gradual change in the index value is shown (control polymers F, G, H, I, L).

[0100] The degree of branching increases with the increase of synthesis temperature.

[0101] Example 7-11 - Second Synthesis of Polymers F, G, H, I, L

[0102] Anhydrous butadiene and solvent dehydrated by passing over a bed ...

Embodiment 12-14

[0103] The preparation of embodiment 12-14-polymer M, N, O

[0104] Anhydrous butadiene and solvent dehydrated by passing over a bed of molecular sieve 3A were fed to the same apparatus as described in the previous example consisting of two 100 liter reactors, each equipped with a scraping wall stirrer and a specific temperature control device, added in a proportion such that the monomer concentration is confirmed to be equal to 12.5%w, and the hourly amount of butadiene is equal to 8kg / hour; the temperature of the monomer-solvent mixture is established at a value not lower than 45°C, and at In any case makes it possible to adjust (together with the amount of steam circulating in the reactor jackets) the temperature of the synthesis in both reactors, which is constant and centered at a value equal to 95°C, varying by no more than 3°C. A mixture of DIBAH and DIBAH-DEAC (1:1 by mole) was fed sequentially through the same feed line, while Nd-tert-carboxylate was fed directly in...

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Abstract

Process for the preparation of polybutadiene effected by the polymerization of butadiene in an aliphatic and/or cyclo-aliphatic solvent in the presence of a catalytic system prepared in situ which comprises: (i) a carboxylate of neodymium soluble in the process solvent containing a variable quantity of water, the H2O/Nd molar ratio ranging from 0.001/1 to 0.50/1; (ii) an alkyl compound of aluminum; (iii) an alkyl compound of aluminum in which at least one bond of Al consists of an Al-Cl bond; The total Al/Nd molar ratio ranging from 4/1 to 12/1, and the Cl/Nd molar ratio ranging from 2/1 to 6/1.

Description

technical field [0001] The present invention relates to a process for the preparation of polybutadiene with a high content of 1,4-cis units in the presence of a catalytic system obtained by reaction between (i) neodymium carboxylates, preferably tertiary Neodymium versatate, (ii) alkyl derivatives of aluminum, (iii) alkylaluminum compounds of chloride, which are directly fed into the reaction environment in an amount such that the amount of Nd is 1-3 mmol / Kg butadiene, and the molar ratio of Al / Nd is 4 / 1-12 / 1, and the molar ratio of Cl / Nd is in the range of 2 / 1:6 / 1. [0002] More specifically, the present invention relates to a process for the preparation of polybutadiene having a high content of 1,4-cis units, which enables simultaneous adjustment of the molecular weight distribution and the degree of branching. In other words, the process of the present invention enables the preparation of branched polybutadiene with a high cis content and a specific molecular weight distri...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/44C08F4/54C08F36/06C08F16/06
CPCC08F36/06C08F4/545B01J31/14C08F4/44C08F4/54
Inventor G·T·维欧拉M·辛纳
Owner POLIMERI EUROPA SPA
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