Hydrogenation catalyst composition, hydrogenated bio-based itaconate rubber, and preparation method and application thereof

Abstract

The present application relates to the field of new materials, in particular to a hydrogenation catalyst composition, a hydrogenated bio-based itaconate rubber, and a preparation method and application thereof.The hydrogenation catalyst composition provided by the present application comprises a hydrogenation catalyst and a ligand; the mass amount of the ligand is 1-20 times that of the hydrogenation catalyst.The present application first uses a homogeneous noble metal complex catalyst composition to perform solution hydrogenation on bio-based itaconate rubber, and has the advantages of less catalyst consumption, high hydrogenation activity and high hydrogenation degree.The polymer after hydrogenation is a novel polymer material, the hydrogenation degree can reach more than 90%, has excellent heat resistance, aging resistance, and excellent processability and physical and mechanical properties, and has a wide application prospect.In the test of the present application, the bio-based itaconate rubber is hydrogenated in an organic solvent by using the hydrogenation catalyst composition of the present application, and the hydrogenation degree reaches 97.2% at the highest.

Description

Technical Field

[0001] This invention relates to the field of new materials, specifically to hydrogenation catalyst compositions, hydrogenated bio-based itaconic acid ester rubber, their preparation methods, and applications. Background Technology

[0002] Bio-based itaconic acid ester rubber (Bio-IBR) is a new generation of high-performance bio-based rubber prepared through free radical emulsion polymerization using bio-based itaconic acid esters as the main monomer. Compared to traditional petroleum-based synthetic rubber, producing 1 ton of bio-based itaconic acid ester rubber can reduce carbon dioxide emissions by approximately 1.4 tons. The market potential for bio-based itaconic acid ester rubber is vast. Furthermore, the research and development and implementation of novel bio-based rubber materials have opened up new paths for the high-quality development and green sustainable development of the rubber industry.

[0003] Bio-based itaconic acid ester rubbers contain carbon-carbon unsaturated bonds in their molecular chains, which limits their application in footwear, conveyor belts, oil pipelines, and other fields. To improve the heat resistance, aging resistance, and operating temperature of polymers with unsaturated bonds, hydrogenation is often used to achieve significant improvements in polymer properties and expand their application areas.

[0004] Numerous reports have been published on selective hydrogenation processes for polymers. Catalysts for the hydrogenation of butadiene-derived rubbers include dicyclopentadiene titanium dichloride for SBS hydrogenation, triisobutylaluminum / nickel isooctanoate for SBS and SIS hydrogenation, and triphenylphosphine rhodium chloride and palladium / carbon catalytic systems for NBR hydrogenation. However, there are currently no literature reports on the use of solution methods for the hydrogenation preparation of hydrogenated bio-based itaconic acid ester rubber (Bio-HIBR). Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a hydrogenation catalyst composition, hydrogenated bio-based itaconic acid ester rubber, a preparation method thereof and its application. The hydrogenation catalyst composition provided by the present invention can hydrogenate bio-based itaconic acid ester rubber in a solution system, with high hydrogenation activity and degree of hydrogenation.

[0006] This invention provides a hydrogenation catalyst composition comprising:

[0007] Hydrogenation catalysts and ligands;

[0008] The mass of the ligand is 1 to 20 times that of the hydrogenation catalyst.

[0009] The hydrogenation catalyst composition provided by this invention is specifically a hydrogenation catalyst composition for bio-based itaconic acid ester rubber. The inventors of this application have inventively discovered that combining a ligand and a hydrogenation catalyst in the hydrogenation of bio-based itaconic acid ester rubber in a solution system exhibits high hydrogenation activity and degree of hydrogenation.

[0010] The ligand in the hydrogenation catalyst composition of the present invention is selected from one of organophosphorus or organobisphosphorus, and more preferably from at least one of triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, 1,3-bis(diphenylphosphine)propane and 1,4-bis(diphenylphosphine)butane. The mass amount of the ligand in the present invention is 1 to 20 times that of the hydrogenation catalyst, preferably 5 to 12 times.

[0011] The hydrogenation catalyst in the hydrogenation catalyst composition of the present invention is selected from at least one of rhodium-based catalysts, ruthenium-based catalysts, palladium-based catalysts, and rhodium-ruthenium-based catalysts, preferably from at least one of rhodium-based catalysts and ruthenium-based catalysts, and more preferably from RhCl(PPh3)3, RhH(PPh)4, RuCl2(PPh3)3, and RuH2(PPh3)4. The hydrogenation catalyst of the present invention is commercially available.

[0012] This invention provides a hydrogenated bio-based itaconic acid ester rubber, which is prepared from hydrogen, bio-based itaconic acid ester rubber, and the aforementioned hydrogenation catalyst composition. The degree of hydrogenation of the hydrogenated bio-based itaconic acid ester rubber provided by this invention is 90% or higher, specifically 93.5% to 97.2%. In one embodiment, the degree of hydrogenation of the hydrogenated bio-based itaconic acid ester rubber provided by this invention is 93.5%, 95.2%, or 97.2%.

[0013] This invention also provides a method for preparing hydrogenated bio-based itaconic acid ester rubber, comprising the following steps: reacting hydrogen, bio-based itaconic acid ester rubber, and the above-mentioned hydrogenation catalyst composition in an organic solvent to obtain hydrogenated bio-based itaconic acid ester rubber. In some embodiments of this invention, hydrogen, bio-based itaconic acid ester rubber, hydrogenation catalyst, and ligand are reacted in an organic solvent to obtain hydrogenated bio-based itaconic acid ester rubber. In some embodiments, bio-based itaconic acid ester rubber is dissolved in an organic solvent to prepare a gel solution, a hydrogenation catalyst and ligand are added thereto, hydrogen is introduced to carry out the reaction, and the product obtained from the reaction is condensed, dehydrated, and dried using a steam condensation method to obtain hydrogenated bio-based itaconic acid ester rubber.

[0014] The amount of hydrogenation catalyst in the hydrogenation catalyst composition of the present invention is 0.02 wt% to 0.20 wt% of the dry weight of the bio-based itaconic acid ester rubber, preferably selected from 0.06% to 0.15%. Therefore, the amount of itaconic acid ester rubber in the present invention can be determined according to actual needs, thereby determining the amount of hydrogenation catalyst in the hydrogenation catalyst composition, and consequently, the amount of ligand. The hydrogenation catalyst and ligand in the present invention are the same as described above and will not be repeated.

[0015] The hydrogen pressure described in this invention is 1.0 MPa to 9.0 MPa. The reaction temperature described in this invention is 40℃ to 120℃, and the reaction time is 1 to 12 hours. The concentration of the bio-based itaconic acid ester rubber solution described in this invention is 5 g / 100 mL to 12 g / 100 mL.

[0016] The bio-based itaconic acid ester rubber of this invention is a copolymer of itaconic acid ester and a conjugated diene, specifically a copolymer obtained by free radical polymerization of itaconic acid ester and a conjugated diene. The conjugated diene in the bio-based itaconic acid ester rubber of this invention is selected from one or two of 1,3-butadiene, isoprene, myrcene, and farnesene. The itaconic acid ester in the bio-based itaconic acid ester rubber of this invention has the structure of Formula I:

[0017]

[0018] Where R1 and R2 are independently C1 to C2. 10 The alkyl groups, R1 and R2, may be the same or different. The itaconic acid ester content in the bio-based itaconic acid ester rubber of the present invention is 10% to 90% by mass, preferably 30% to 70%, and more preferably 50% to 70%.

[0019] This invention relates to hydrogenated bio-based itaconic acid ester rubber obtained by hydrogenation of bio-based itaconic acid ester rubber via a solution method. The bio-based itaconic acid ester rubber undergoes hydrogenation in the presence of at least an organic solvent, a hydrogenation catalyst, and a ligand. The resulting hydrogenated bio-based itaconic acid ester rubber is prepared in the same manner as described above and will not be repeated here. The organic solvent used in this invention is selected from one or a mixture of benzene, toluene, xylene, or chlorobenzene.

[0020] The present invention also provides the application of the above-mentioned hydrogenated bio-based itaconic acid ester rubber or the hydrogenated bio-based itaconic acid ester rubber prepared by the above-mentioned preparation method in the fields of footwear materials, conveyor belts or oil pipelines.

[0021] This invention provides a hydrogenation catalyst composition, hydrogenated bio-based itaconic acid ester rubber, its preparation method, and its applications. The hydrogenation catalyst composition provided by this invention comprises a hydrogenation catalyst and a ligand; the mass amount of the ligand is 1 to 20 times that of the hydrogenation catalyst. This invention is the first to use a homogeneous noble metal complex catalyst composition for solution hydrogenation of bio-based itaconic acid ester rubber, which has the advantages of low catalyst dosage, high hydrogenation activity, and high degree of hydrogenation. The hydrogenated polymer, hydrogenated bio-based itaconic acid ester rubber, is a novel polymer material with a degree of hydrogenation reaching over 90%. This hydrogenated polymer exhibits excellent heat resistance, anti-aging properties, and excellent processability and physical and mechanical properties, showing broad application prospects. Detailed Implementation

[0022] This invention discloses a hydrogenation catalyst composition, a hydrogenated bio-based itaconic acid ester rubber, its preparation method, and its applications. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired results. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments, and those skilled in the art will clearly be able to modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0023] The bio-based itaconic acid ester rubbers used in the various embodiments of the present invention are copolymers obtained by free radical polymerization of diethyl itaconic acid and butadiene.

[0024] In this invention, the degree of unsaturation of itaconic acid ester rubber before and after hydrogenation is determined by iodometric titration, the method of which is specified in national standard GB-1776-81. The formula for calculating the degree of hydrogenation is as follows:

[0025] Degree of hydrogenation = [(Unsaturation of polymer before hydrogenation - Unsaturation of polymer after hydrogenation) / Unsaturation of polymer before hydrogenation] × 100%.

[0026] The present invention will be further described below with reference to the embodiments:

[0027] Example 1

[0028] 100g of bio-based itaconic acid ester rubber (50% diethyl itaconic acid, denoted as IBR-1#) was dissolved in 1500ml of toluene and added to a 2L high-pressure reactor, which was purged with nitrogen three times. 0.15g of catalyst and 1.5g of triphenylphosphine were added to the reactor, and hydrogen gas was introduced to initiate the reaction. The reaction temperature was 85℃, the hydrogen pressure was 4.0MPa, and the reaction time was 10 hours. The hydrogenated solution was then subjected to steam flocculation and drying to obtain hydrogenated bio-based itaconic acid ester rubber (denoted as HIBR-1#). The degree of hydrogenation of HIBR-1# was determined to be 93.5% using iodometric titration.

[0029] Example 2

[0030] 100g of bio-based itaconic acid ester rubber (60% diethyl itaconic acid, denoted as IBR-2#) was dissolved in 1250ml of chlorobenzene and added to a 2L high-pressure reactor, which was purged with nitrogen three times. 0.12g of catalyst and 1.5g of triphenylphosphine were added to the reactor, and hydrogen gas was introduced to initiate the reaction. The reaction temperature was 100℃, the hydrogen pressure was 4.0MPa, and the reaction time was 8 hours. The hydrogenated rubber solution was then subjected to steam flocculation and drying to obtain hydrogenated bio-based itaconic acid ester rubber (denoted as HIBR-2#). The degree of hydrogenation of HIBR-2# was determined to be 95.2% using the iodometric method.

[0031] Example 3

[0032] 100g of bio-based itaconic acid ester rubber (70% diethyl itaconic acid, denoted as IBR-3#) was dissolved in 1000ml of chlorobenzene and added to a 2L high-pressure reactor, which was purged with nitrogen three times. 0.1g of catalyst and 1g of triphenylphosphine were added to the reactor, and hydrogen gas was introduced to initiate the reaction. The reaction temperature was 90℃, the hydrogen pressure was 6.0MPa, and the reaction time was 10 hours. The hydrogenated solution was then subjected to steam flocculation and drying to obtain hydrogenated bio-based itaconic acid ester rubber (denoted as HIBR-3#). The degree of hydrogenation of HIBR-3# was determined to be 97.2% using the iodometric method.

[0033] The mechanical properties of HIBR-1#, HIBR-2#, and HIBR-3# prepared after hydrogenation were compared with those of IBR-1#, IBR-2#, and IBR-3# before hydrogenation according to GB / T528-2009. The aging performance was tested in an aging chamber. The results are shown in Table 1. Table 1 is a comparison of the properties of hydrogenated bio-based itaconic acid ester rubber before and after hydrogenation.

[0034] Table 1

[0035]

[0036] As shown in Table 1, the hydrogenated bio-based itaconic acid ester rubber not only has excellent mechanical properties, but also significantly improved anti-aging properties.

[0037] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A process for the preparation of hydrogenated bio-based itaconate ester rubber, characterized in that, The method comprises the following steps: reacting hydrogen, bio-based itaconate rubber and a hydrogenation catalyst composition in an organic solvent to obtain a hydrogenated bio-based itaconate rubber; The hydrogenation catalyst composition comprises: a hydrogenation catalyst selected from at least one of RhCl(PPh3)3, RhH(PPh)4, RuCl2(PPh3)3, RuH2(PPh3)4, and a ligand selected from at least one of triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane; The mass amount of the ligand is 1-20 times of the hydrogenation catalyst.

2. The production method according to claim 1, characterized by, The mass amount of the ligand is 5-12 times of the hydrogenation catalyst.

3. The preparation method according to claim 1, characterized in that, The amount of the hydrogenation catalyst in the hydrogenation catalyst composition is 0.02 wt%-0.20 wt% of the dry rubber weight of the bio-based itaconate rubber.

4. The method of claim 1, wherein, The bio-based itaconate rubber is a copolymer of itaconate and conjugated diene; The conjugated diene in the bio-based itaconate rubber is selected from one or two of 1,3-butadiene, isoprene, myrcene and farnesene; The itaconate in the bio-based itaconate rubber has the structure of Formula I: Formula I; wherein R1and R2are independently C1-C 10 alkyl, R1and R2are the same or different.

5. Hydrogenated bio-based itaconate ester rubber, characterized in that, obtained by the preparation method of any one of claims 1-4.

6. Use of the hydrogenated bio-based itaconate rubber of claim 5 in the field of shoe materials, conveyor belts or oil pipelines.

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