Polyols and Polyurethanes from Hydroformylation of Soybean Oil

Andrew Guo

doi:10.1023/A:1021022123733

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Polyols and Polyurethanes from Hydroformylation of Soybean Oil

Andrew Guo

2002, Journal of Polymers and The Environment

https://doi.org/10.1023/A:1021022123733

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Abstract

This paper compares physical and mechanical properties of polyurethanes derived via the hydroformylation approach and is a part of our study on the structure–property relationships in polyurethanes created from vegetable oils. The double bonds of soybean oil are first converted to aldehydes through hydroformylation using either rhodium or cobalt as the catalyst. The aldehydes are hydrogenated by Raney nickel to alcohols, forming a triglyceride polyol. The latter is reacted with polymeric MDI to yield the polyurethane. Depending on the degree of conversion, the materials can behave as hard rubbers or rigid plastics. The rhodium-catalyzed reaction afforded a polyol with a 95% conversion, giving rise to a rigid polyurethane, while the cobalt-catalyzed reaction gives a polyol with a 67% conversion, leading to a hard rubber having lower mechanical strengths. Addition of glycerine as a cross-linker systematically improves the properties of the polyurethanes. The polyols are characterized by DSC. The measured properties of polyurethanes include glass transition temperatures, tensile strengths, flexural moduli, and impact strengths.

FAQs

What explains the different mechanical properties of rhodium and cobalt-derived polyurethanes?add

The study demonstrates that polyurethanes from rhodium-derived polyols exhibit a higher glass transition temperature (Tg) above room temperature, indicating rigidity, while cobalt-derived materials have a Tg around or below room temperature, behaving as hard rubber.

How does the catalyst choice affect the hydroformylation process efficiency?add

Rhodium catalyst yields a higher conversion under mild conditions, but cobalt catalyst is more cost-effective despite requiring harsher conditions and resulting in lower conversion.

When are vegetable oil-derived polyols advantageous for industrial applications?add

The paper reveals that polyols produced via hydroformylation can serve as renewable materials for polyurethanes, with specific applications influenced by their hardness and elasticity provided by catalyst choice.

What are the calorimetric differences between rhodium and cobalt polyols?add

Differential scanning calorimetry (DSC) showed that cobalt-derived polyols have melting peaks only 4 degrees higher than rhodium-derived polyols, indicating similar thermal behaviors despite variations in the synthesis process.

Why does adding glycerine affect polyurethane rigidity?add

The addition of a polyhydroxyl cross-linker like glycerine significantly increases the rigidity of polyurethanes by enhancing cross-linking density, as demonstrated in the tested formulations of the study.

Figures (9)

Table II. Glass Transition Temperatures (Tg) of the Soy Polyurethanes Derived from the Rhodium- and Cobalt-Catalyzed Hydroformylation

Table III. Tensile Properties of the Soy Polyurethanes Derived from the Rhodium- and Cobalt-Catalyzed Hydroformylation Fig. 1. Stress-strain curves of polyurethanes derived from the rhodium- and cobalt-catalyzed hydroformylation of soybean oil.

Table I. Chemical and Physical Properties of the Soy Polyols Derived from the Rhodium- and Cobalt-Catalyzed Hydroformylation EXPERIMENTAL hydrogenation reaction, for the hydroformylation step and lead sion of the olefins. Because conversion is ble oils. The rhodium reaction gives high conversion of the olefins under mild conditions, but the catalyst is more expensive and requires a second metal (nickel) for the hydrogenation step. On the other hand is cheaper and does not require a second metal for the , the cobalt catalyst but it requires harsh conditions of functionality of the polyol molecule, the cross- density of the polyurethanes varies accordingly (T Asaresult, the polyure thanes derived from the hy mylated soy polyols behave as a rigid plastic rhodium process and a hard rubber for the cobalt process. This phenomenon is re peratures shown in Tabl ties, shown in Table II e 2, as well as the tensile and Fig. 1, of the polyure The Tg of the polyure process is above room temperature, thus it is a fair s to alower conver- a direct measure inking able I). drofor- for the ected in the glass transition tem- proper- thanes. thane derived from the rhodium y rigid

Fig. 2. DSC curves of the cobalt-derived polyol and the Rhodium- derived polyol as compared to soybean oil. Polyurethanes from Soybean Oil Hydroformylation

Table IV. DSC Data of the Cobalt-Derived Polyol and the Rhodium- Derived Polyol as Compared to Soybean Oil

Fig. 5. Flexural moduli of polyurethanes derived from the rhodium- catalyzed hydroformylated soy polyol with varying amount of glycerine. Fig. 4. Tensile strengths of polyurethanes derived from the rhodium- catalyzed hydroformylated soy polyol with varying amount of glycerine.

Fig. 3. DSC Tgs of polyurethanes derived from the rhodium-catalyzed hydroformylated soy polyol with varying amount of glycerine.

Fig. 6. Impact strengths of polyurethanes derived from the rhodium- catalyzed hydroformylated soy polyol with varying amount of glycerine. REFERENCES

References (16)

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Polyols and Polyurethanes from Hydroformylation of Soybean Oil

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