CN116174037A - Catalyst for selectively partially hydrogenating conjugated diene polymer and preparation method thereof - Google Patents
Catalyst for selectively partially hydrogenating conjugated diene polymer and preparation method thereof Download PDFInfo
- Publication number
- CN116174037A CN116174037A CN202111421553.0A CN202111421553A CN116174037A CN 116174037 A CN116174037 A CN 116174037A CN 202111421553 A CN202111421553 A CN 202111421553A CN 116174037 A CN116174037 A CN 116174037A
- Authority
- CN
- China
- Prior art keywords
- conjugated diene
- catalyst
- component
- hydrogenation
- polymers according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a catalyst for selectively partially hydrogenating conjugated diene polymer and a preparation method thereof, belonging to the technical field of catalytic hydrogenation of conjugated diene polymer, wherein the catalyst comprises a component A: organometallic compounds and/or metal complexes of elements of group VIII, component B: organometallic compound, component C: and a nitrogen-containing heterocyclic compound, which hydrogenates conjugated diene double bonds on short side chains in the conjugated diene polymer segment. The invention realizes selective partial hydrogenation of conjugated diene double bonds by adding nitrogen-containing basic micromolecules into a group VIII metal compound and/or a complex and an organic metal compound to form a complex catalytic system.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation of conjugated diene polymers, and particularly relates to a catalyst for selectively partially hydrogenating conjugated diene polymers and a preparation method thereof.
Background
The block copolymer thermoplastic elastomer of butadiene and/or isoprene and styrene can be widely used for plastic modification, asphalt modification, shoe materials, adhesives, sealants, optical cable ointments, finger-sticking agents, packaging films and the like. Since such conjugated diene polymers contain a large amount of unsaturated double bonds, they generally have the advantage of crosslinking reaction such as functionalization, grafting and vulcanization in application, but they are also greatly limited in aging resistance and weather resistance and are not excellent in compatibility with plastics and the like. Therefore, the polymer is often hydrogenated appropriately to reduce the number of unsaturated double bonds so as to obtain better characteristics, improve the ageing resistance and weather resistance of the polymer and widen the application field of materials.
The copolymers are generally subjected to so-called "selective hydrogenation" in order to increase the thermo-oxidative stability and weatherability of the copolymers. "Selective hydrogenation" is defined as hydrogenation primarily of conjugated diene monomers. In the copolymer having "conjugated diene monomer", "vinyl aromatic monomer", the hydrogenation rate of unsaturated double bonds of the vinyl aromatic monomer is much lower than that of the conjugated diene. The hydrogenation rate of unsaturated double bonds of the conjugated diene monomer is at least 95%, even more than 98%; the hydrogenation rate of benzene ring double bond of vinyl aromatic monomer is lower than 5%, even lower than 2%.
The most of the catalysts used in the current industrialized application for the selective hydrogenation of the styrene-conjugated diene copolymer are homogeneous catalysts, and most of the catalysts are metallocene titanium catalysts or aluminum-nickel catalysts. For example, CN1332183A, CN1410465A, CN1844178A and other catalytic systems mainly adopt a cyclopentadienyl titanium compound as a main catalyst and alkyl lithium and phthalate as cocatalysts; or a catalytic system such as CN 105085724, CN103087221, CN106563503A and the like which mainly adopts Ni or Co organic acid salt as a main catalyst and alkyl aluminum compounds as a cocatalyst. The raw materials of the latter type of catalyst are easy to obtain, the preparation method of the catalyst is simple and mature, and particularly, the polymers containing isoprene units such as styrene-isoprene copolymer and styrene-isoprene-butadiene copolymer are selectively hydrogenated, so that hydrogenation products with high hydrogenation degree are easier to obtain, and the application of the catalyst is wider.
By introducing a third component, namely an aging promoter, into the aluminum nickel or aluminum cobalt catalytic system, the stability and hydrogenation efficiency of the catalyst can be improved. U.S. patent No. 4207409 discloses that in an aluminum-nickel catalyst system, a small amount of water is added to improve the activity and hydrogenation efficiency of the catalyst, and EP0360356 reports that organonickel is combined with a small amount of water and then reacts with aluminum alkyl to improve the catalyst activity. CN106540747B is added with alcohols or lipids or a mixture of the alcohols or lipids and water in batches in a nickel-aluminum or cobalt-aluminum catalyst system as an ageing promoter, so that the preparation and ageing time of the catalyst are shortened, and the activity of the catalyst is improved. Similarly, CN107597189a achieves the same objective by introducing a third component of conjugated diene during the aging process of catalyst preparation, achieving "selective hydrogenation" efficiency, i.e., the hydrogenation rate of unsaturated double bonds of conjugated diene monomer is 98% or more, and the hydrogenation rate of benzene ring double bonds of vinyl aromatic monomer is less than 5%.
However, the research of CN111087496A shows that the benzene ring of the styrene-isoprene segmented copolymer still contains unsaturated double bonds after selective hydrogenation, and the solubility parameter difference between the benzene ring and saturated linear alkane is large, so that the obtained hydrogenated segmented copolymer has poor transparency and cannot be used in the occasion with high transparency requirement. To obtain a hydrogenated block copolymer with better transparency, this patent incorporates water and a substituted or unsubstituted C1-C12 mono-or polyol in an aluminum nickel catalyst system. The hydrogenation degree of the benzene ring of the styrene section is improved to be more than 98 percent while the hydrogenation degree of the isoprene section is kept to be more than 98 percent, so-called selective hydrogenation is broken through, and complete hydrogenation is realized.
However, the organic nickel and/or cobalt and alkyl aluminum mixed components adopted in the hydrogenation reaction process of the conjugated diene polymer in the prior art have higher activity in the early stage of hydrogenation reaction, the reaction speed is higher, and the olefinic bond (namely vinyl double bond) on the short side chain of the activated hydrogenated conjugated diene segment is basically consistent with the olefinic bond on the conjugated diene main chain, so that the selectivity cannot be controlled.
Disclosure of Invention
Based on the technical problems, the invention provides a catalyst for selectively partially hydrogenating conjugated diene polymers and a preparation method thereof, wherein a complex catalytic system is formed by adding nitrogen-containing basic small molecules into a VIII group metal compound and/or a complex and an organic metal compound, so that the selective partial hydrogenation of conjugated diene double bonds is realized. The catalyst has a hydrogenation rate of 95% or more of conjugated diene double bonds (so-called vinyl double bonds) on short side chains in the conjugated diene polymer chain segment, and a hydrogenation rate of 10% or less of conjugated diene double bonds on the main chain, and a hydrogenation rate of 1% or less of benzene ring double bonds of the vinyl aromatic monomer.
In order to achieve the above object, the present invention is realized by the following technical scheme:
a catalyst for the selective partial hydrogenation of conjugated diene polymers, said catalyst comprising component a: organometallic compounds and/or metal complexes of elements of group VIII, component B: organometallic compound, component C: and a nitrogen-containing heterocyclic compound, which hydrogenates conjugated diene double bonds on short side chains in the conjugated diene polymer segment.
Further, the catalyst has a double bond hydrogenation rate of not less than 95% for a conjugated diene on a short side chain in a conjugated diene polymer segment, a double bond hydrogenation rate of not more than 10% for a conjugated diene on a main chain, and a double bond hydrogenation rate of not more than 1% for a benzene ring of a vinyl aromatic monomer.
Further, the component a: the organometallic compound and/or complex of group VIII element is naphthenate, octanoate, 2-ethylhexyl salt or acetylacetone complex containing one or more of Fe, co, ni, rh, pd, pt.
Further, the component A is one or more of nickel naphthenate, nickel isooctanoate, nickel 2-ethylhexanoate and nickel acetylacetonate, and cobalt naphthenate, cobalt isooctanoate, cobalt 2-ethylhexanoate and cobalt acetylacetonate.
Further, the component B: the metal organic compound is one or more of triethylaluminum, triisobutylaluminum, n-butyllithium and sec-butyllithium.
Further, the component C: the nitrogen-containing heterocyclic compound is one or more of pyridine, alkyl substituted pyridine, pyrazine and N-methylpyrole.
Further, the molar ratio of component a to component B is 1:1-4, the molar ratio of component A to component C is 1:1-6.
Further, the catalyst is used in an amount of 0.01 to 0.1g of metal per 100g of conjugated diene polymer.
Further, the conjugated diene polymer comprises a homopolymer of a conjugated diene monomer or a random copolymer or a block copolymer of a combination of a conjugated diene monomer and a vinyl aromatic monomer. The homopolymer or copolymer may have 3 or more microstructure unit compositions, such as 1,2, cis-1, 4, trans-1, 4 microstructures, and possibly 3,4 microstructures (isoprene participates in polymerization) due to the difference in polymerized monomers.
A process for preparing the catalyst used to selectively partially hydrogenate conjugated diene polymer includes such steps as proportionally adding component A, component B, component C and inertial solvent to reactor under the condition of inertial gas, ageing at 10-80 deg.C for 5-30 min.
The hydrogenation conditions include: the hydrogenation temperature is 40-80 ℃, and the hydrogenation pressure is 0.5-2.0MPa.
In particular, there may be 3 or more microstructure unit compositions, such as 1,2, cis-1, 4, trans-1, 4 microstructures, and possibly 3,4 microstructures (isoprene participates in polymerization), in the conjugated diene homopolymer or the styrene conjugated diene copolymer due to the difference in polymerized monomers.
Specifically, the monomer proportion of the styrene conjugated diene copolymer is 5-80% of styrene and 95-20% of conjugated diene.
Specifically, the 1,2 and/or 3,4 structure content in the microstructure of the styrene conjugated diene copolymer accounts for 30-70% of the conjugated diene monomer.
According to the invention, a great amount of experiments are carried out to carry out a great amount of research and modification on catalytic hydrogenation reaction, and the invention discovers that a nitrogen-containing alkaline micromolecule such as a nitrogen-containing heterocyclic compound is added into a hydrogenation reaction system according to a certain proportion to form a Ni and/or Co-N-Al complex catalytic system with nickel and/or cobalt and aluminum alkyl; in particular to pyridine, pyrazine and other common cheap compounds, and can realize selective partial hydrogenation of conjugated diene double bonds.
The invention has the advantages and beneficial effects that:
the catalyst promoter adopted by the invention not only can control the hydrogenation activity and selectivity at the initial stage of the reaction, but also can shorten the hydrogenation reaction time and reduce the catalyst usage amount, and can ensure that the hydrogenation rate of conjugated diene double bonds (so-called vinyl double bonds) on short side chains in a polymer chain segment is more than 95%, the hydrogenation rate of conjugated diene double bonds on a main chain is controlled to be less than 10%, and the hydrogenation rate of benzene ring double bonds of vinyl aromatic monomers is controlled to be less than 1%. Thus providing a "selectively partially hydrogenated" hydrogenated block copolymer having a wide range of uses.
The catalyst disclosed by the invention has the advantages that the cocatalyst is a nitrogenous alkaline micromolecule, and after the reaction is finished, the alkaline cocatalyst is recovered while the metal ions in the polymer are washed by a dilute acid solution, so that pollution is avoided.
Drawings
FIG. 1 is a schematic representation of a selectively partially hydrogenated SBS block copolymer of example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and examples, but the scope of the invention is not limited thereto. Those skilled in the art can and should appreciate that any simple changes or substitutions based on the true spirit of the invention should fall within the scope of the invention as hereinafter claimed.
A catalyst for the selective partial hydrogenation of conjugated diene polymers, said catalyst comprising component a: organometallic compounds and/or metal complexes of elements of group VIII, component B: organometallic compound, component C: and a nitrogen-containing heterocyclic compound, which hydrogenates conjugated diene double bonds on short side chains in the conjugated diene polymer segment.
Specifically, the catalyst has a hydrogenation rate of 95% or more of double bonds of a conjugated diene in a short side chain in a conjugated diene polymer segment, a hydrogenation rate of 10% or less of double bonds of a conjugated diene in a main chain, and a hydrogenation rate of 1% or less of double bonds of a benzene ring of a vinyl aromatic monomer.
Component A: the organometallic compound and/or complex of group VIII element is naphthenate, octanoate, 2-ethylhexyl salt or acetylacetone complex containing one or more of Fe, co, ni, rh, pd, pt. Preferably one or more of nickel naphthenate, nickel isooctanoate, nickel 2-ethylhexanoate, nickel acetylacetonate, cobalt naphthenate, cobalt isooctanoate, cobalt 2-ethylhexanoate and cobalt acetylacetonate. Component B: the metal organic compound is one or more of triethylaluminum, triisobutylaluminum, n-butyllithium and sec-butyllithium. Component C: the nitrogen-containing heterocyclic compound is one or more of pyridine, alkyl substituted pyridine, pyrazine and N-methylpyrole.
The molar ratio of component B to component A is 1:1-4, the molar ratio of component C to component A being 1:1-6. The catalyst is used in an amount of 0.01 to 0.1g of metal per 100g of conjugated diene polymer.
A process for preparing the catalyst used to selectively partially hydrogenate conjugated diene polymer includes such steps as proportionally adding component A, component B, component C and inertial solvent to reactor under the condition of inertial gas, ageing at 10-80 deg.C for 5-30 min. Specifically, the components A, B are respectively diluted by inert solvents, sequentially added into a reaction kettle and aged at 60 ℃ for 60min. Then adding the component C and continuously aging for 30min at 60 ℃ to obtain the hydrogenation catalyst. Component a metal, calculated on a molar basis of metal and pyridine: metal of component B: component c=1:2:1-4.
Example 1
(1) Preparation of Linear triblock SBS copolymer
Under inert atmosphere, adding 2.7 kg of refined cyclohexane into a 5-liter stainless steel stirring kettle, starting stirring and heating to enable the temperature to reach 60 ℃, adding 50 g of styrene, 2 ml of 5%wt tetramethyl ethylenediamine and diethylene glycol dimethyl ether composite structure regulator solution (the molar ratio of the two is 1:2), and 6 ml of 0.5mol/L n-butyl lithium solution to initiate reaction for 60min; then 200 g butadiene is added to continue the reaction at 60 ℃ for 120min; finally 50 g of styrene are added and reacted still at 60℃for 60min. After the polymerization is finished, the base glue solution is completely transferred into a 5 liter hydrogenation kettle, and is terminated by introducing 0.5MPa hydrogen at 70 ℃ for 20min. And (3) taking a small amount of SBS glue solution and separating out the polymer by using absolute ethyl alcohol. The polymer prepared was analyzed by GPC, having a molecular weight of 10.2 tens of thousands and a polydispersity of 1.02. The microstructure of the polymer is analyzed by adopting hydrogen nuclear magnetism, the content of the block styrene is 99 percent, and the content of 1,2-PB is 42 percent.
(2) Preparation of hydrogenation catalyst
Cobalt naphthenate and triisobutylaluminum were diluted with cyclohexane solvent to obtain a cobalt naphthenate solution (component A) and a triisobutylaluminum solution (component B) at a concentration of 0.2mol/L, respectively.
Adding cobalt naphthenate solution with the concentration of 0.2mol/L into a 100mL reaction kettle fully replaced by high-purity nitrogen, slowly adding triisobutyl aluminum solution with the concentration of 0.1mol/L under stirring, and aging for 60min at 60 ℃; then adding 0.5mol/L pyridine solution (component C), and aging for 30min at 60 ℃ to obtain a hydrogenation catalyst, wherein Co is calculated by mol of metal and pyridine: al: pyridine=1: 2:3.
(3) Polymer hydrogenation
After the hydrogen termination of the basic glue solution, the temperature of the hydrogenation kettle is maintained at 70 ℃. The catalyst prepared above was added, immediately after which hydrogen was introduced to maintain the pressure at 2.0MPa and the reaction was continued with stirring for 1 hour, with a hydrogenation catalyst loading of 0.05g Co per 100g polymer. And (3) separating out a small amount of hydrogenated glue solution from the polymer by using absolute ethyl alcohol, drying, and analyzing the microstructure hydrogenation degree of the polymer by adopting hydrogen nuclear magnetism, wherein the hydrogenation degree of 1,2-PB is 96.2%, the hydrogenation degree of 1,4-PB is 7.9%, and the hydrogenation degree of benzene ring is less than 1%.
Co-Al system or Ni-Al system catalyst, which has hydrogenation function, is Co or Ni, and Al has the function of reducing Co or Ni to an active state of +1 valence, and possibly reducing to be excessive to 0 valence, and has no activity. So Al: the Co molar ratio is generally 2 to 6. The pyridine has the function of forming a complex with metal Co-Al to weaken an active center, and meanwhile, the pyridine can play a role of selective partial hydrogenation due to the steric hindrance of the self space structure of the high-molecular polymer.
Example 2
The detailed procedure of example 2 is similar to that of example 1, except that catalyst component A: the molar ratio of the component C is fixed at 1:2:2, the hydrogenation degree of the microstructure of the hydrogenated polymer is analyzed by adopting hydrogen nuclear magnetism, the hydrogenation degree of 1,2-PB is 98.5%, the hydrogenation degree of 1,4-PB is 9.1%, and the hydrogenation degree of benzene ring is less than 1%.
Example 3
The detailed procedure of example 3 is similar to that of example 1, except that catalyst component A: the molar ratio of the component C is fixed at 1:2:1, the hydrogenation degree of the microstructure of the hydrogenated polymer is analyzed by adopting hydrogen nuclear magnetism, the hydrogenation degree of 1,2-PB is 99.1%, the hydrogenation degree of 1,4-PB is 9.8%, and the hydrogenation degree of benzene ring is less than 1%.
Example 4
The procedure of example 4 was similar to that of example 1, except that the polymer prepared was analyzed by GPC and had a molecular weight of 22.5 ten thousand and a polydispersity of 1.03. The microstructure of the polymer is analyzed by adopting hydrogen nuclear magnetism, the content of the block styrene is 99.2 percent, and the content of 1,2-PB is 39 percent. The catalyst component A comprises the following components: the molar ratio of the component C is fixed at 1:2:2, the hydrogenation degree of the microstructure of the hydrogenated polymer is analyzed by adopting hydrogen nuclear magnetism, the hydrogenation degree of 1,2-PB is 97.8%, the hydrogenation degree of 1,4-PB is 9.2%, and the hydrogenation degree of benzene ring is less than 1%.
Example 5
The detailed procedure of example 5 is similar to that of example 1 except that catalyst component A is nickel naphthenate and catalyst component A comprises component B: the molar ratio of the component C is fixed at 1:2:4, the hydrogenation degree of the microstructure of the hydrogenated polymer is analyzed by adopting hydrogen nuclear magnetism, the hydrogenation degree of 1,2-PB is 99.8%, the hydrogenation degree of 1,4-PB is 9.7%, and the hydrogenation degree of benzene ring is less than 1%.
Example 7
The procedure of example 7 is similar to that of example 1 except that catalyst component C is pyrazine and catalyst component A is component B: the molar ratio of the component C is fixed at 1:2:2, the hydrogenation degree of the microstructure of the hydrogenated polymer is analyzed by adopting hydrogen nuclear magnetism, the hydrogenation degree of 1,2-PB is 98.1%, the hydrogenation degree of 1,4-PB is 8.4%, and the hydrogenation degree of benzene ring is less than 1%.
Example 8
Preparation of triblock SIS copolymer, hydrogenation
The specific procedure was similar to example 1, using an anionic polymerization method with cyclohexane as an inert solvent, n-butyllithium as an initiator, and isopropyl alcohol as a terminator, a styrene-isoprene-styrene triblock copolymer (SIS) was prepared in a polymerization reactor. The concentration of the glue solution is 10%, the number average molecular weight of the block copolymer is 12 ten thousand, the weight ratio of styrene to isoprene monomer units is 35:65, and the content of polydisperse coefficient 1.03,3,4-PI is 45%. The catalyst component A comprises the following components: the molar ratio of the component C is fixed at 1:2:2.5, the hydrogenation degree of the microstructure of the hydrogenated polymer is analyzed by adopting hydrogen nuclear magnetism, the hydrogenation degree of 3,4-PI is 99.0%, the hydrogenation degree of 1,4-PI is 9.6%, and the hydrogenation degree of benzene ring is less than 1%.
Comparative example 1
(1) Preparation of Linear triblock SBS copolymer
Under inert atmosphere, adding 2.7 kg of refined cyclohexane into a 5-liter stainless steel stirring kettle, starting stirring and heating to enable the temperature to reach 60 ℃, adding 50 g of styrene, 2 ml of 5%wt tetramethyl ethylenediamine and diethylene glycol dimethyl ether composite structure regulator solution (the molar ratio of the two is 1:2), and 6 ml of 0.5mol/L n-butyl lithium solution to initiate reaction for 60min; then 200 g butadiene is added to continue the reaction at 60 ℃ for 120min; finally 50 g of styrene are added and reacted still at 60℃for 60min. After the polymerization is finished, the base glue solution is completely transferred into a 5 liter hydrogenation kettle, and is terminated by introducing 0.5MPa hydrogen at 70 ℃ for 20min. And (3) taking a small amount of SBS glue solution and separating out the polymer by using absolute ethyl alcohol. The polymer prepared was analyzed by GPC, having a molecular weight of 10.2 tens of thousands and a polydispersity of 1.02. The microstructure of the polymer is analyzed by adopting hydrogen nuclear magnetism, the content of the block styrene is 99 percent, and the content of 1,2-PB is 42 percent.
(2) Preparation of hydrogenation catalyst
Cobalt naphthenate and triisobutylaluminum were diluted with cyclohexane solvent to obtain a cobalt naphthenate solution (component A) and a triisobutylaluminum solution (component B) at a concentration of 0.2mol/L, respectively.
Adding cobalt naphthenate solution with the concentration of 0.2mol/L into a 100mL reaction kettle fully replaced by high-purity nitrogen, slowly adding triisobutyl aluminum solution with the concentration of 0.1mol/L under stirring, and aging for 60min at 60 ℃; a hydrogenation catalyst is obtained, co is calculated according to metal mole: al=1: 2.
(3) Polymer hydrogenation
After the hydrogen termination of the basic glue solution, the temperature of the hydrogenation kettle is maintained at 70 ℃. The catalyst prepared above was added, immediately after which hydrogen was introduced to maintain the pressure at 2.0MPa and the reaction was continued with stirring for 1 hour, with a hydrogenation catalyst loading of 0.05g Co per 100g polymer. And (3) separating out a small amount of hydrogenated glue solution from the polymer by using absolute ethyl alcohol, drying, and analyzing the microstructure hydrogenation degree of the polymer by adopting hydrogen nuclear magnetism, wherein the hydrogenation degree of 1,2-PB is 98.3%, the hydrogenation degree of 1,4-PB is 96.5%, and the hydrogenation degree of benzene ring is less than 1%.
It was thus demonstrated that in a catalyst system without pyridine, almost all of the conjugated diene segments would be hydrogenated, i.e., the 1,2-PB and 1,4-PB had a hydrogenation degree of 95% or more.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention; all such equivalent changes and modifications that do not depart from the spirit of the invention are intended to be included within the scope of the present invention as set forth in the appended claims.
Claims (10)
1. A catalyst for selectively partially hydrogenating a conjugated diene polymer, characterized by: the catalyst comprises a component A: organometallic compounds and/or metal complexes of elements of group VIII, component B: organometallic compound, component C: and a nitrogen-containing heterocyclic compound, which hydrogenates conjugated diene double bonds on short side chains in the conjugated diene polymer segment.
2. The catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 1, characterized in that: the catalyst has a hydrogenation rate of 95% or more for conjugated diene double bonds on short side chains in conjugated diene polymer segments, a hydrogenation rate of 10% or less for conjugated diene double bonds on main chains, and a hydrogenation rate of 1% or less for benzene ring double bonds of vinyl aromatic monomers.
3. The catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 1, characterized in that: the component A comprises the following components: the organometallic compound and/or complex of group VIII element is naphthenate, octanoate, 2-ethylhexyl salt or acetylacetone complex containing one or more of Fe, co, ni, rh, pd, pt.
4. A catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 3, characterized in that: the component A is one or more of nickel naphthenate, nickel isooctanoate, nickel 2-ethylhexanoate, nickel acetylacetonate, cobalt naphthenate, cobalt isooctanoate, cobalt 2-ethylhexanoate and cobalt acetylacetonate.
5. The catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 1, characterized in that: the component B comprises the following components: the metal organic compound is one or more of triethylaluminum, triisobutylaluminum, n-butyllithium and sec-butyllithium.
6. The catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 1, characterized in that: the component C: the nitrogen-containing heterocyclic compound is one or more of pyridine, alkyl substituted pyridine, pyrazine and N-methylpyrole.
7. The catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 1, characterized in that: the molar ratio of the component A to the component B is 1:1-4, the molar ratio of component A to component C is 1:1-6.
8. The catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 1, characterized in that: the catalyst is used in an amount of 0.01 to 0.1g of metal per 100g of conjugated diene polymer.
9. The catalyst for the selective partial hydrogenation of conjugated diene polymers according to claim 1, characterized in that: the conjugated diene polymer comprises a homopolymer of conjugated diene monomer or a random copolymer or a block copolymer of a combination of conjugated diene monomer and vinyl aromatic monomer.
10. The process for preparing a catalyst for selectively partially hydrogenating conjugated diene polymers according to any one of claims 1 to 9, characterized in that: under the condition of inert gas, adding the component A, the component B, the component C and the inert solvent into a reaction bottle according to the metering ratio, and aging at the reaction temperature of 10-80 ℃ for 5-30min to obtain the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111421553.0A CN116174037A (en) | 2021-11-26 | 2021-11-26 | Catalyst for selectively partially hydrogenating conjugated diene polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111421553.0A CN116174037A (en) | 2021-11-26 | 2021-11-26 | Catalyst for selectively partially hydrogenating conjugated diene polymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116174037A true CN116174037A (en) | 2023-05-30 |
Family
ID=86447542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111421553.0A Pending CN116174037A (en) | 2021-11-26 | 2021-11-26 | Catalyst for selectively partially hydrogenating conjugated diene polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116174037A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565875A (en) * | 1969-03-10 | 1971-02-23 | Goodrich Gulf Chem Inc | Polymerization process and catalyst system therefor |
| FR2187730A1 (en) * | 1972-06-05 | 1974-01-18 | Inst Francais Du Petrole | Selective hydrogenation of hydrocarbons - using organonickel cpds with reducing agents as catalysts |
| US4188348A (en) * | 1978-08-11 | 1980-02-12 | The Goodyear Tire & Rubber Company | Hydrogenation of cyclopentadiene to form cyclopentene |
| ITMI20022055A1 (en) * | 2002-09-27 | 2004-03-28 | Enitecnologie Spa | PROCEDURE FOR HYDROGENATION OF HOMOPOLYMERS AND COPOLYMERS OF CONJUGATE DIENES. |
| WO2011108672A2 (en) * | 2010-03-04 | 2011-09-09 | 高砂香料工業株式会社 | Homogeneous asymmetric hydrogenation catalyst |
| CN104945541A (en) * | 2014-03-27 | 2015-09-30 | 中国石油化工股份有限公司 | Selective hydrogenation method for conjugated diene polymers |
| EP3081572A1 (en) * | 2015-04-16 | 2016-10-19 | ARLANXEO Deutschland GmbH | Ruthenium-or osmium-based complex catalysts |
| CN106563503A (en) * | 2016-10-25 | 2017-04-19 | 山东聚圣科技有限公司 | Ternary catalysis system used for selective hydrogenation of conjugated diene containing polymer and application thereof |
| CN109181813A (en) * | 2018-07-31 | 2019-01-11 | 沈阳化工研究院有限公司 | A kind of star viscosity index improver and preparation method thereof for lubricating oil |
| CN112142883A (en) * | 2019-06-28 | 2020-12-29 | 沈阳化工研究院有限公司 | Continuous hydrogenation method and device for conjugated diene polymer |
| US20210198385A1 (en) * | 2018-04-20 | 2021-07-01 | Arlanxeo Deutschland Gmbh | Hydrogenation catalyst compositions and their use for hydrogenation of nitrile rubber |
-
2021
- 2021-11-26 CN CN202111421553.0A patent/CN116174037A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565875A (en) * | 1969-03-10 | 1971-02-23 | Goodrich Gulf Chem Inc | Polymerization process and catalyst system therefor |
| FR2187730A1 (en) * | 1972-06-05 | 1974-01-18 | Inst Francais Du Petrole | Selective hydrogenation of hydrocarbons - using organonickel cpds with reducing agents as catalysts |
| US4188348A (en) * | 1978-08-11 | 1980-02-12 | The Goodyear Tire & Rubber Company | Hydrogenation of cyclopentadiene to form cyclopentene |
| ITMI20022055A1 (en) * | 2002-09-27 | 2004-03-28 | Enitecnologie Spa | PROCEDURE FOR HYDROGENATION OF HOMOPOLYMERS AND COPOLYMERS OF CONJUGATE DIENES. |
| WO2011108672A2 (en) * | 2010-03-04 | 2011-09-09 | 高砂香料工業株式会社 | Homogeneous asymmetric hydrogenation catalyst |
| CN104945541A (en) * | 2014-03-27 | 2015-09-30 | 中国石油化工股份有限公司 | Selective hydrogenation method for conjugated diene polymers |
| EP3081572A1 (en) * | 2015-04-16 | 2016-10-19 | ARLANXEO Deutschland GmbH | Ruthenium-or osmium-based complex catalysts |
| CN106563503A (en) * | 2016-10-25 | 2017-04-19 | 山东聚圣科技有限公司 | Ternary catalysis system used for selective hydrogenation of conjugated diene containing polymer and application thereof |
| US20210198385A1 (en) * | 2018-04-20 | 2021-07-01 | Arlanxeo Deutschland Gmbh | Hydrogenation catalyst compositions and their use for hydrogenation of nitrile rubber |
| CN109181813A (en) * | 2018-07-31 | 2019-01-11 | 沈阳化工研究院有限公司 | A kind of star viscosity index improver and preparation method thereof for lubricating oil |
| CN112142883A (en) * | 2019-06-28 | 2020-12-29 | 沈阳化工研究院有限公司 | Continuous hydrogenation method and device for conjugated diene polymer |
Non-Patent Citations (2)
| Title |
|---|
| MASATO OHASHI ET AL.: "Nickel-Catalyzed Dehydrogenative [4 + 2] Cycloaddition of 1, 3-Dienes with Nitriles", 《 J. AM. CHEM. SOC.》, vol. 133, no. 45, 17 October 2011 (2011-10-17), pages 18018 - 18021 * |
| 贺小进 等: "添加剂对镍系催化苯乙烯- 丁二烯- 苯乙烯 嵌段共聚物加氢的影响", 《合成橡胶工业》, vol. 27, no. 6, 25 November 2004 (2004-11-25), pages 337 - 340 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114075307B (en) | Rare earth catalyst and preparation method and application thereof | |
| CN1177599A (en) | Preparation for catalyst for hydrogenation of styrene-butadieno copolymer | |
| CN111085271B (en) | Hydrogenation catalyst for producing hydrogenated styrene-conjugated diene copolymer, method for producing hydrogenation catalyst, hydrogenation method, and hydrogenated copolymer | |
| CN110903423A (en) | Rare earth catalyst, preparation method and application thereof | |
| CN101580560A (en) | Catalyst system and method for polymerizing butadiene | |
| US3899474A (en) | Process for manufacturing hydrogenated polymers from conjugated diolefins | |
| WO2023050789A1 (en) | Iron-based conjugated diene polymer and preparation method therefor | |
| CN108219046A (en) | Rare earth catalyst and preparation method and application thereof | |
| KR100298571B1 (en) | A process for preparation of high 1,4-cis polybutadiene | |
| CN104945541B (en) | A kind of method of selective hydrogenation of conjugated diolefine polymer | |
| CN104231133B (en) | A kind of rare earth catalyst and the method being used for preparing cis conjugated diene polymer thereof | |
| CN107200797B (en) | Preparation method of polymer | |
| CN111087495B (en) | Hydrogenation catalyst for producing hydrogenated styrene-conjugated diene copolymer, method for producing hydrogenation catalyst, hydrogenation method, and hydrogenated copolymer | |
| CN112175124B (en) | Efficient preparation method of high molecular weight polylaurene with high 1, 4-structure content | |
| CN116174037A (en) | Catalyst for selectively partially hydrogenating conjugated diene polymer and preparation method thereof | |
| CN112266432B (en) | Efficient preparation method of high molecular weight polylaurene with high 3, 4-structure content | |
| CN104624236A (en) | Hydrogenation catalyst for olefine unsaturated bond containing polymer, preparation method and hydrogenation reaction method thereof | |
| CN106188356A (en) | A kind of Tetraheteropoly rare earth catalyst system and catalyzing and its preparation method and application | |
| CN1476451A (en) | Method for making selectvely hydrogenated block copolymers of vinyl aromatic hydrocarbons and conjugated dienes | |
| CN115073666B (en) | High molecular weight iron-based bio-based rubber, preparation method and application thereof, and rubber composition based on high molecular weight iron-based bio-based rubber | |
| CN101153069B (en) | A kind of preparation method of high cis-butadiene benzene block copolymer | |
| CN106977656B (en) | Dendritic polydiene rubber and preparation method thereof | |
| CN113278119B (en) | Hydrogenated styrene-butadiene block copolymer and preparation method and application thereof | |
| CN115873045B (en) | N,N-bidentate carboxylic acid iron complex and preparation method thereof and application thereof in conjugated diene polymerization | |
| CN118684804A (en) | A method for preparing ultra-low vinyl liquid polybutadiene rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |