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CN-121988356-A - Hydrogenation catalyst, preparation method and application thereof, hydrogenated styrene-butadiene-styrene block copolymer and preparation method thereof

CN121988356ACN 121988356 ACN121988356 ACN 121988356ACN-121988356-A

Abstract

The invention belongs to the technical field of catalysts, and particularly relates to a hydrogenation catalyst, a preparation method and application thereof, a hydrogenated styrene-butadiene-styrene block copolymer and a preparation method thereof. The hydrogenation catalyst has excellent hydrogen activating capacity, can have high hydrogenation degree when being used for the hydrogenation of styrene polymers, has mild hydrogenation conditions and small structural change of the polymers, and can be used for large-scale industrial production.

Inventors

  • LIN FENG
  • WANG YUCHAO
  • XIE TINGTING
  • GONG GUANGBI
  • WU LIPING
  • ZHENG HONGBING
  • HAN YAN
  • FENG YUZHI
  • WEN JINGBIN
  • CHEN FEI

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (20)

  1. 1. A hydrogenation catalyst comprising a support and an active component supported on the support, the active component comprising a non-noble metal phosphide and noble metal clusters deposited on the non-noble metal phosphide.
  2. 2. The hydrogenation catalyst of claim 1, wherein, The molar ratio of non-noble metal phosphide to phosphorus on the surface of the catalyst is 2-6:1, and/or The non-noble metal content is 5-70wt% based on the total mass of the catalyst, and/or The content of noble metal is 0.05-2wt%, based on the total mass of the catalyst, and/or The active component is contained in an amount of 5 to 95wt%, based on the total mass of the catalyst, and/or The carrier is present in an amount of 5 to 95 wt.%, based on the total mass of the catalyst, and/or The diameter of the carrier is 100 nm-100 mu m.
  3. 3. The hydrogenation catalyst according to claim 2, wherein, The molar ratio of non-noble metal phosphide to phosphorus on the surface of the catalyst is 3.5-4.5:1, and/or The non-noble metal content is 10-50wt% based on the total mass of the catalyst, and/or The content of noble metal is 0.1-1wt%, based on the total mass of the catalyst, and/or The carrier is present in an amount of 29 to 90wt% based on the total mass of the catalyst.
  4. 4. The hydrogenation catalyst according to claim 3, wherein, The non-noble metal content is 10-40wt% based on the total mass of the catalyst, and/or The content of noble metal is 0.2-0.5wt% based on the total mass of the catalyst, and/or The carrier is present in an amount of 49.5 to 90wt% based on the total mass of the catalyst.
  5. 5. The hydrogenation catalyst of claim 1, wherein, The carrier is at least one selected from inorganic oxides, natural minerals and carbon substances.
  6. 6. The hydrogenation catalyst according to claim 5, wherein, The inorganic oxide is at least one selected from silicon dioxide, aluminum oxide, titanium dioxide, cerium oxide, zirconium oxide and magnesium oxide, and/or The natural mineral is selected from at least one of diatomite, clay, diatom and pumice, and/or The carbon material is selected from activated carbon and/or graphite.
  7. 7. The hydrogenation catalyst according to any one of claim 1 to 6, wherein, The non-noble metal in the non-noble metal phosphide is selected from transition metal elements and/or lanthanoids, and/or The noble metal is selected from at least one of iridium, ruthenium, rhodium, platinum and palladium.
  8. 8. The hydrogenation catalyst of claim 7 wherein the catalyst is, The transition metal element is selected from the group consisting of group VIB element, group VIII element and group IIIB element, and/or The lanthanoid is at least one selected from cerium, lanthanum, and praseodymium.
  9. 9. The hydrogenation catalyst of claim 8 wherein the catalyst is selected from the group consisting of, The group VIB element being selected from molybdenum and/or tungsten, and/or The group VIII element is selected from at least one of iron, nickel, cobalt, copper and manganese, and/or The group IIIB element is selected from yttrium.
  10. 10. The hydrogenation catalyst of claim 7 wherein the catalyst is, The non-noble metal contains at least nickel, and/or The noble metal contains at least platinum.
  11. 11. A process for preparing a hydrogenation catalyst according to any one of claims 1 to 10, which comprises: s1, a solution containing a non-noble metal source, a structure regulator, a phosphorus-containing reducing agent and water is contacted with a carrier to carry out a first precipitation reaction to obtain a first material; s2, carrying out a second precipitation reaction on the first material and a noble metal source in the presence of a reducing agent; s3, drying and roasting the solid phase matters in the second precipitation reaction.
  12. 12. The preparation method according to claim 11, wherein, In step S1, the structure regulator is selected from compounds containing acid ion and/or ammonium ion, and/or In step S1, the phosphorus-containing reducing agent is selected from at least one of hypophosphite, hypophosphite and phosphite, and/or In step S2, the reducing agent includes at least one of hypophosphite, phosphite, sodium borohydride, ascorbic acid, ascorbate, and tartrate.
  13. 13. The preparation method according to claim 12, wherein, The structure regulator is selected from alkali metal salt corresponding to at least one of acetic acid, citric acid, ethylenediamine tetraacetic acid, oxalic acid, lactic acid, malic acid and tannic acid, and/or The phosphorous-containing reducing agent is selected from hypophosphites.
  14. 14. The preparation method according to claim 11, wherein, The mass ratio of the structure regulator to the non-noble metal source is 0.3-3:1, and/or The non-noble metal source is calculated as non-noble metal element, the content of the non-noble metal source in the solution is 2-100 g/L, and/or The content of the phosphorus-containing reducing agent in the solution is 1-50 g/L based on phosphorus element, and/or The content of carrier in the solution is 10-200 g/L, and/or The non-noble metal source is calculated as non-noble metal element, the noble metal source is calculated as noble metal element, the mass ratio of the noble metal source to the non-noble metal source is 0.001-0.1:1, and/or The mass ratio of the reducing agent to the noble metal source is 10-15:1 based on noble metal element.
  15. 15. The process according to any one of claim 11 to 14, wherein, The reaction conditions of the first precipitate and the second precipitate each independently include: Under inert atmosphere, and/or PH of 8-14, and/or The reaction temperature is 20-90 ℃; And/or The first precipitation reaction takes place for a period of time of from 30 to 180 min, and/or The second precipitation reaction time is 10-120 min.
  16. 16. The process according to any one of claim 11 to 14, wherein, In step S3, the roasting conditions include: in a reducing atmosphere, and/or At a temperature of 200-650 ℃, and/or The time is 1-10 h.
  17. 17. Use of a hydrogenation catalyst according to any one of claims 1-10 for the hydrogenation of styrenic polymers.
  18. 18. The use according to claim 17, wherein, The styrenic polymer is selected from at least one copolymer produced by copolymerizing at least one styrenic comonomer and at least one comonomer of a C4 to C8 conjugated diene monomer.
  19. 19. The use according to claim 18, wherein, The structure of the styrene polymer is a block structure.
  20. 20. The use according to claim 19, wherein, The structure of the styrene polymer is triblock.

Description

Hydrogenation catalyst, preparation method and application thereof, hydrogenated styrene-butadiene-styrene block copolymer and preparation method thereof Technical Field The invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst, a preparation method and application thereof, and a hydrogenated styrene-butadiene-styrene block copolymer and a preparation method thereof. Background The cyclic block copolymer (Cyclic Block Copolymer, abbreviated as CBC) is a novel polymer material obtained by completely hydrogenating a block copolymer of styrene and a conjugated diene (typically, triblock styrene-butadiene-styrene block copolymer SBS). The fully hydrogenated CBC has a crystallizable polyethylene block and an amorphous polycyclohexyl ethylene segment, and the mechanical physical properties of the CBC material can be effectively regulated and controlled by adjusting the proportion of the soft block structure and the hard block structure in the copolymer, thereby meeting the performance requirements of different products. In addition, the CBC material has high transparency, high fluidity, low density, low moisture absorption, low impurity content, excellent thermal oxygen stability and excellent UV transmissivity, is suitable for processing technologies such as extrusion, injection molding, blow molding and the like, and has great application potential in the aspects of optical devices, capacitance diaphragms, medical materials, IC (integrated circuit) processing devices and the like. Currently, CBC production processes can be generally divided into two modules, an anionic polymerization and a catalytic hydrogenation module, respectively. Anionic polymerization technology has been a very mature process in the market since the proposal of living anions in the fifth sixties of the last century, and has developed very rapidly based on non-polar monomers such as styrene and butadiene. In contrast, the perhydrogenation technology is a key difficulty in the CBC production flow, and the catalyst with excellent hydrogenation performance is the core of the whole technology. Currently, hydrogenation technology for solution polymerized styrene-butadiene rubber in the market mainly realizes hydrogenation saturation of butadiene segments, reports on hydrogenation technology of benzene ring structures in high polymers are very few, industrial production of SBS full hydrogenation technology is realized by only one enterprise of Taiwan poly company in China worldwide, and a production line with 5000 tons of CBC annual production can be put into production in 2018, and the product serial name is ViviOnTM. The polymer hydrogenation catalyst can be classified into a homogeneous catalyst and a heterogeneous catalyst. Homogeneous catalysts, because of poor thermal stability, are typically used for hydrogenation of carbon-carbon double bonds at temperatures in the range of 60-120 ℃. Heterogeneous catalysts are mainly aromatic hydrogenation catalysts, and related documents mainly include ：CN107250188A、CN103665282A、CN116948118A、CN1171913C、TWI660975B、CN101768229B、CN104511295B、EP0378104A2、CN116948063A、CN115364876A and the like. However, the catalyst has complex structural design, high noble metal content and high use cost. Meanwhile, the heterogeneous hydrogenation catalyst reported in the prior patent requires longer reaction time and higher reaction temperature in the use process, so that side reactions such as molecular chain breakage and the like occur in the reaction process, and the performance of the final CBC product is affected. The efficient thixotropic enzyme perhydrogenation technology of Taiwan polymerization company in China is transferred from the Dow chemical technology, and the technology adopts a specially designed macroporous carrier and a high-load noble metal-based active center, so that good hydrogenation effect of SBS base gum is realized, but the preparation technology of the catalyst is complex, and meanwhile, the production cost of CBC is increased. Therefore, research and development of a low-loading noble metal catalyst with low cost and excellent catalytic performance for hydrogenation of styrene polymers are of great significance. Disclosure of Invention The invention aims to solve the problems of complex structural design, high noble metal content, high use cost and the like of a benzene ring structure hydrogenation technology and the problems of the prior art, and provides a hydrogenation catalyst and a preparation method thereof. In order to achieve the above object, the first aspect of the present invention provides a hydrogenation catalyst comprising a carrier and an active component supported on the carrier, the active component containing a non-noble metal phosphide and noble metal clusters deposited on the non-noble metal phosphide. The second aspect of the present invention provides a method for producing a hydrogenation catalyst, the method comprising: s1, a